High structural and optical quality InxGa1−xP/GaAs quantum wells, with x from 0.51 to 0.45, have been successfully grown by atomic layer molecular beam epitaxy. In that compositional range, an important blue shift of the quantum well luminescence lines is observed, which is explained by an increase of the conduction band gap offset from compressive to tensile strain conditions. The luminescence intensity decreases with temperature above 20–30 K, which is attributed to impurities located at the interfaces and inside the quantum wells. The influence of the In content on the oscillator strength of the optical transitions is also evaluated.