Yes, the hub is identical
Same 5x112 PCD and same 66.6 mm centre bore: wheels from Mercedes GLS-Classe bolt on and centre on Mercedes S-Classe W221 S63 AMG 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 Mercedes GLS-Classe is compared with the one from Mercedes S-Classe W221 S63 AMG 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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8.5Jx19 ET62.5 · 275/55R19 — Check on the car
Compared with the original ≈8Jx19 ET43 on Mercedes S-Classe W221 S63 AMG: shock absorber side +25.9 mm, wheel arch side −13.2 mm, tyre diameter +14.3 % : fit it with the original tyre size of Mercedes S-Classe W221 S63 AMG (255/40R19), not that of Mercedes GLS-Classe.
Comparison for guidance only (estimated width). Check in detail
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8Jx18 ET56.5 · 265/60R18
Mercedes S-Classe W221 S63 AMG has no 18-inch original wheel in our data: check the approved fitments and caliper clearance.
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 Mercedes S-Classe W221 S63 AMG (M14x1.50), 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 Mercedes S-Classe W221 S63 AMG on Mercedes GLS-Classe?