Yes, the hub is identical
Same 5x100 PCD and same 57.1 mm centre bore: wheels from Pontiac Sunfire bolt on and centre on Volkswagen Polo AW without rings. You still need to check the offset and tyres, detailed below.
≈: width estimated from the original tyre size.
Wheel by wheel: offset and tyres
Each original wheel from Pontiac Sunfire is compared with the one from Volkswagen Polo AW of the same diameter: how much closer the wheel gets to the shock absorber or how far it sticks out of the wheel arch, and whether the tyre keeps the same overall diameter.
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≈6Jx14 ET42 · 195/70R14 — Check on the car
Compared with the original 5Jx14 ET38 on Volkswagen Polo AW: shock absorber side +16.7 mm, wheel arch side +8.7 mm, tyre diameter +2.3 % : fit it with the original tyre size of Volkswagen Polo AW (185/70R14), not that of Pontiac Sunfire.
Comparison for guidance only (estimated width). Check in detail
Before fitting the wheels
An identical hub is not enough: offset, width and diameter change the position of the wheel, and larger calipers can touch a smaller wheel. Original wheels often use bolts or nuts with a specific seat: keep the fixings intended for the wheel, with the thread of Volkswagen Polo AW (M14x1.5), tightened to the torque shown on its vehicle page. Finally, check that the size is among the approved fitments for your vehicle. This comparison is for guidance only: have the fitting approved by a professional.
And the other way round: wheels from Volkswagen Polo AW on Pontiac Sunfire?