The GaP crystal quality and Si bulk lifetime of GaP/Si heterostructures, grown by molecular beam epitaxy, are investigated. The Si bulk lifetime is reduced by over one order of magnitude after thermal deoxidation at high temperatures (>700°C). This significant reduction of the bulk lifetime is not observed when 150nm-thick SiNx film is present on the backside of Si wafer, which can act as a diffusion barrier and/or getter. In addition, a 15nm-thick GaP layer grown on the front side of Si wafer with SiNx on the backside shows a high crystal quality of GaP with a low crystalline defect density of 1.1×105cm−2. Moreover, the Si bulk lifetime is determined to be 1.83ms with a-Si:H passivation at an injected minority-carrier density of 1×1015cm−3, indicative of no bulk lifetime degradation. The high crystallinity of GaP and improved Si bulk lifetime are beneficial to improve photovoltaic device performance of III–V compound solar cells integrated with Si solar cells.