Low-temperature plasma enhanced atomic layer deposition (PE-ALD) was successfully used to grow silicon (Si) doped amorphous and microcrystalline gallium phosphide (GaP) layers onto p-type Si wafers for the fabrication of n-GaP/p-Si heterojunction solar cells. PE-ALD was realized at 380 °C with continuous H2 plasma discharge and the alternate use of phosphine and trimethylgallium as sources of P and Ga atoms, respectively. The layers were doped with silicon thanks to silane (SiH4) diluted in H2 that was introduced as a separated step. High SiH4 dilution in H2 (0.1%) allows us to deposit stoichiometric GaP layers. Hall measurements performed on the GaP:Si/p-Si structures reveal the presence of an n-type layer with a sheet electron density of 6–10 × 1013 cm−2 and an electron mobility of 13–25 cm2 V−1 s−1 at 300 K. This is associated with the formation of a strong inversion layer in the p-Si substrate due to strong band bending at the GaP/Si interface. GaP:Si/p-Si heterostructures exhibit a clear photovoltaic effect, with the performance being currently limited by the poor quality of the p-Si wafers and reflection losses at the GaP surface. This opens interesting perspectives for Si doped GaP deposited by PE-ALD for the fabrication of p-Si based heterojunction solar cells.