This study deposits nitrogenated carbon (C:N) films on p-type silicon (p-Si) substrates to fabricate C:N/p-Si photovoltaic solar cells by thermal chemical vapor deposition. Pure acetylene and nitrogen were used as the precursor gases. The deposition temperatures were set to 720, 730, 740, and 750 degrees C. The chemical composition, microstructure, mechanical and electrical properties of C:N films prepared at different deposition temperatures were studied. The results show that when the deposition temperature is 730 degrees C, the C:N/p-Si photovoltaic solar cell has the best photovoltaic parameters, in which the open-circuit voltage, short-circuit current, fill factor, and conversion efficiency are 120 mV, 1.59 mA, 30.1%, and 0.06%, respectively. This preliminary result also shows that C:N films with large amounts of highly ordered graphite-like structures, high N doping content, and low electrical resistivity are suitable to fabricate C:N/p-Si photovoltaic solar cells.