Photoluminescence (PL) measurements were carried out on 0.5-μm thick BaSi 2 epitaxial films grown on Si(111) substrates with various Ba-to-Si deposition rate ratios (R Ba /R Si ) in the range of 1.7-5.1. The samples were excited from both the frontside (BaSi 2 ) and the backside (Si substrate), at temperatures in the range of 8-50 K. These measurements have highlighted the existence of localized states within the bandgap that result from defects in the BaSi 2 films. The PL intensity is highly dependent on the excitation power, temperature, and R Ba /R Si . Of those studied, the BaSi 2 film at R Ba /R Si =4.0 showed the most intense PL and weak photoresponsivity, whereas the PL intensity was weaker for the other samples. Therefore, we chose this sample for a detailed PL investigation. Based on the results we determined the energy separation between localized states, corresponding to PL peak energies. The difference in PL spectra excited from the BaSi 2 -side and Si-side is attributed to the difference in kinds of defects emitting PL. The photoresponsivity of the BaSi 2 was drastically enhanced by atomic hydrogen passivation, and the PL intensity of the sample decreased accordingly.