In this article, indium phosphide (InP) layers were grown using the method of plasma-chemical atomic layer deposition on crystalline silicon substrates for the first time. Trimethyllindium (TMI) was used as a source of indium, and phosphine (PH3) was used as a source of phosphorus. Properties of InP layers were evaluated, such as structural properties, electrical conductivity, type of conductivity and carrier concentration to integrate them into a c-Si-based solar cell. Root-Mean-Square (RMS) roughness measurements showed that the use of intermediate annealing in Ar plasma after the stage of deposition of a phosphorus monolayer leads to a significant decrease in roughness to the level of fractions of nanometers. The composition of the InP layers according to the energy dispersive X-ray spectroscopy (EDX) was close to stoichiometric. The measurements of dark IV characteristics showed that the InP layer has a donor type of conductivity. I–V characteristics of InP/p-Si structure under solar spectrum illumination, show open circuit voltage of Voc = 0.48 V. Van der Pauw measurements demonstrate high concentration of carriers and their high mobility. Thus, the possibility of using InP-based layers for solar cells was shown.