Integration of the III–V material systems on Si is an enabling technology for achieving high efficiency heterojunction Si-based photovoltaic devices. Gallium phosphide (GaP) offers numerous potential electrical, optical, and material advantages over amorphous silicon (a-Si) for the realization of several heterojunction solar cell designs. In this paper, details are given for the growth, fabrication, and characterization of different n-GaP/n-Si heterojunction solar cells to explore the effect of GaP as a carrier-selective contact. The cell performance is promising with high Si bulk lifetime (∼2.2 ms at the injection level of 1015 cm−3) and an open-circuit voltage of 618 mV and an efficiency of 13.1% in this new solar cell design. In addition to GaP as an electron-selective contact, MoO
was successfully implemented as a hole-selective contact in the n-GaP/n-Si heterojunction solar cell, increasing efficiency to 14.1% by improving the short wavelength response. The Si bulk lifetime is maintained during growth of GaP on Si by two different approaches and their effects on GaP/Si solar cell performance are also presented.