Reducing the surface reflectivity of silicon substrates is essential for preparing high-performance Si-based solar cells. We synthesized pyramid-nanowire-structured Si (Si-PNWs) anti-reflection substrates, which have excellent light-trapping ability (<4% reflectance). Furthermore, diethyl phthalate (DEP), a water-insoluble phthalic acid ester, was applied to optimize the Si-PNWs/PEDOT:PSS interface; the photoelectric conversion efficiency of heterojunction solar cells was shown to increase from 9.82% to 13.48%. We performed a detailed examination of the shape and optical characteristics of Si-PNWs, as well as associated photoelectric performance tests, to investigate the origin of performance improvements in Si-PNWs/PEDOT:PSS heterojunction solar cells (HSCs).