Yes, the hub is identical
Same 5x114.3 PCD and same 60.1 mm centre bore: wheels from Toyota Prius Wagon bolt on and centre on Toyota Highlander 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 Toyota Prius Wagon is compared with the one from Toyota Highlander 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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6.5Jx16 ET39 · 205/60R16 — Fits like the original
Compared with the original ≈7Jx16 ET35 on Toyota Highlander: shock absorber side −2.3 mm, wheel arch side −10.4 mm, tyre diameter −9.6 % : fit it with the original tyre size of Toyota Highlander (225/70R16), not that of Toyota Prius Wagon.
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 Toyota Highlander (Ecrous - 12x1.50), 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 Toyota Highlander on Toyota Prius Wagon?