Low‐temperature photoluminescence (PL) measurements of GaAs, AlxGa1−xAs, and AlAs samples grown by molecular beam epitaxy have been carried out to study the effects of hydrogen diffusion. Following exposure to a hydrogen plasma, the PL spectra of AlxGa1−xAs change. In particular, direct gap AlxGa1−xAs shows a strong increase in the total PL intensity whereas the PL spectra of indirect gap AlxGa1−xAs show an increase in the excitonic‐related recombinations after hydrogenation; the binary compounds present less dramatic changes. We interpret our results in terms of hydrogen passivation of deep and shallow centers (DX), whose densities are higher for aluminum concentration near the direct to the indirect gap crossover.