Using low-temperature molecular beam epitaxy, we study substitutions of Fe atoms for Co ones in Co_3-xFe_xSi Heusler-compound films grown on Si and Ge. Even for the low-temperature grown Heusler-compound films, the Co-Fe atomic substitution at A and C sites can be confirmed by the conversion electron Mossbauer spectroscopy measurements. As a result, the magnetic moment and room-temperature spin polarization estimated by nonlocal spin-valve measurements are systematically changed with the Co-Fe substitutions. This study experimentally verified that the Co-Fe substitution in Co_3-xFe_xSi Heusler compounds can directly affect the room-temperature spin polarization.