Yes, the hub is identical
Same 4x108 PCD and same 65.1 mm centre bore: wheels from DS DS 3 bolt on and centre on Alfa Romeo Junior 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 DS DS 3 is compared with the one from Alfa Romeo Junior 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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≈7Jx17 ET42 · 215/65R17 — Check on the car
Compared with the original ≈7Jx17 ET35 on Alfa Romeo Junior: shock absorber side +7 mm, wheel arch side −7 mm, tyre diameter +3.1 % : fit it with the original tyre size of Alfa Romeo Junior (215/60R17), not that of DS DS 3.
Comparison for guidance only (estimated width). Check in detail
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≈6Jx16 ET25 · 195/55R16
Alfa Romeo Junior has no 16-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 Alfa Romeo Junior (M12x1.25), 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 Alfa Romeo Junior on DS DS 3?