The effect of hydrogen-surfactant-mediated molecular beam epitaxy (MBE) growth of Ge1−
x
Sn
x
layer on Ge(001) substrate on crystalline quality and photoluminescence (PL) property has been investigated. The effect of irradiation of atomic hydrogen (H) generated by dissociating molecular hydrogen (H2) were examined during the MBE growth. H irradiation significantly improves the surface morphology with the enhancement of the two-dimensional growth of the Ge1−
x
Sn
x
epitaxial layer. Enhanced diffuse scattering is observed in the X-ray diffraction profile, indicating a high density of point defects. In the PL spectrum of the H2-irradiated Ge1−
x
Sn
x
layer, two components are observed, suggesting the radiative recombination with both indirect and direct transitions, while one component related to the direct transition is observable in the H-irradiated sample. The postdeposition annealing in nitrogen ambient at as low as 220 °C decreases the PL intensity of the H-irradiated Ge1−
x
Sn
x
layer, although the intensity is recovered after annealing at 300 °C, suggesting the annihilation of point defects in the Ge1−
x
Sn
x
layer.