1991 Pontiac 6000 LE ( Canadian ) Rear window de fogger not work

Yes, the switch is the next thing to check.

https://www.google.com/search?q=2008+pontiac+grand+prix+rear+defogger+not+working

https://fuse-box.info/pontiac/pontiac-grand-prix-2004-2008-fuses-and-relays

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System Description NEEL0216 MODELS WITHOUT POWER DOOR LOCKS NEEL0216S01 The rear window defogger system is controlled by the rear window defogger timer. The rear window defogger operates only for approximately 15 minutes. The rear window defogger switch is integral to the air control. Power is supplied at all times
to rear window defogger relay terminal 5
through 20A fuse [No. 25, located in the fuse block (J/B)]. With the ignition switch in the ON or START position, power is supplied
through 10A fuse [No. 5, located in the fuse block (J/B)]
to rear window defogger relay terminal 1, and
to rear window defogger timer terminal 1. Ground is supplied to air control (rear window defogger switch) terminal 8 and rear window defogger timer terminal 4 through body grounds M14 and M68. With the rear window defogger switch (located in air control) ON, ground is supplied
to rear window defogger timer terminal 3
through air control (rear window defogger switch) terminal 8. Rear window defogger timer terminal 2 then supplies ground to the rear window defogger relay terminal 2. With power and ground supplied, the rear window defogger relay is energized. Power is supplied
through terminal 3 of the rear window defogger relay
to rear window defogger terminal +. Rear window defogger terminal - is grounded through body ground R102. With power and ground supplied, the rear window defogger filaments heat and defog the rear window. When the system is activated, the rear window defogger indicator illuminates in the air control. Power is supplied
from rear window defogger relay terminal 3
to air control (rear window defogger switch) terminal 4. Air control terminal 8 is grounded through body grounds M14 and M68. MODELS WITH POWER DOOR LOCKS NEEL0216S02 The rear window defogger system is controlled by the smart entrance control unit. The rear window defogger operates only for approximately 15 minutes. The rear window defogger switch is integral to the air control. Power is supplied at all times
to rear window defogger relay terminal 5
through 20A fuse [No. 25, located in the fuse block (J/B)] and
to smart entrance control unit terminal 49
through 7.5A fuse [No. 28, located in the fuse block (J/B)]. With the ignition switch in the ON or START position, power is supplied
through 10A fuse [No. 5, located in the fuse block (J/B)]
to rear window defogger relay terminal 1 and
to smart entrance control unit terminal 27. Ground is supplied to air control (rear window defogger switch) terminal 8 and smart entrance control unit terminals 43 and 64 through body grounds M14 and M68. With the rear window defogger switch (located in air control) ON, ground is supplied
to smart entrance control unit terminal 14
through air control (rear window defogger switch) terminal 1. Smart entrance control unit terminal 37 then supplies ground to the rear window defogger relay terminal 2. With power and ground supplied, the rear window defogger relay is energized. Power is supplied
through terminal 3 of the rear window defogger relay
to rear window defogger terminal +.
Rear window defogger terminal - is grounded through body ground R102. With power and ground supplied, the rear window defogger filaments heat and defog the rear window. When the system is activated, the rear window defogger indicator illuminates in the air control. Power is supplied
from rear window defogger relay terminal 3
to air control (rear window defogger switch) terminal 4. Air control (rear window defogger switch) terminal 8 is grounded through body grounds M14 and M68

you can try out some guide from here reliable-store
they also provide live cha t feature for instant help and it's very useful

I found this. Your heated mirror also works off that relay. You can do ohms test on the grid, if the grid is open, no continuity. The auto store should sell a product to paint over the open spot to restore continuity, if you can find the open spot.
Not trying to cause trouble, just killing time. Have a good day.

rear window defogger ? it is fused in your fuse box ! and has a relay to activate the rear fogger ...right ?

that or a possible vacuum leak

you may find it in the fuse box under the hood, try looking under the hood for the fuse box it may be there......cheers.

have you looked at your fuses and the connector onto window defogger sometimes rist clean the connection and try that see how it goes good luck

There is a module that controls the rear window defogger grid . LGM/ EGM Liftgate or endgate module .Receive's message on class 2 serial data network from the HVAC control module to turn it on when button pressed . Fuse # 3 30 amp located in the rear fuse box . Do you know where the rear fuse box is ?
Rear Window Defogger Description and Operation
Rear Window Defogger System Components
The rear window defogger system consist of the following components:
• HVAC control module
• Liftgate module (LGM)/endgate module (EGM)
• Rear window defogger grid
Rear Window Defogger Operation (With LGM)
Battery positive voltage is supplied through the LGM 2 fuse to the LGM for the rear window defogger system. When the rear window defogger switch is depressed, the HVAC control module illuminates the rear window defogger indicator, and sends a class 2 message to the LGM to enable the rear window defogger. The LGM enables the rear window defogger by allowing battery positive voltage to the rear window defogger.
When the rear window defogger switch is pressed for the first time, the defogger cycle lasts 10 minutes. Further operation results in 10 minute defogger cycles.
Rear Window Defogger Operation (With EGM)
Battery positive voltage is supplied through the EGM 2 fuse to the EGM for the rear window defogger system. When the rear window defogger switch is depressed, the HVAC control module illuminates the rear window defogger indicator, and sends a class 2 message to the EGM to enable the rear window defogger. The EGM enables the rear window defogger by allowing battery positive voltage to the rear window defogger.
The following conditions must be met for rear window defogger to operate:
• The end gate glass position is not below the index position.
• The window express down movement is not requested.
• The window down movement is not requested.
If the end-gate glass is not fully closed, the DIC displays "Tailgate Glass Down" when the rear defogger operation is attempted.
When the rear window defogger switch is pressed for the first time, the defogger cycle lasts 10 minutes. Further operation results in 10 minute defogger cycles.

Fuse Block - Rear
Beneath the left rear seat

check grids along rear window to check for broken lines and check wires on both sides of glass where connections are.