Heteroepitaxial single crystalline films of GaP, GaAs, and InAs are grown on Si (100) and (111) substrates by laser vacuum epitaxy (LVE). Photoelectric properties as well as I–U and C–U characteristics and Hall mobilities in the LVE grown AIIIBv–Si heterojunctions are measured. High electron mobility (3000 cm2 V−1 s−1) and high efficiency (21%) are obtained for the InAs–Si heterojunction with a lattice mismatch of the components of about 11%. The band diagrams according to the experimental data are constructed. Carrier transport mechanisms and the specific features of the LVE process are discussed.