We demonstrate a solar cell based on n-type nanoporous Si (PSi) filled with copper phthalocyanine (CuPC) and its derivatives (including a discotic liquid crystal form). The CuPC device shows conversion efficiency up to 2% under white light illumination (20–30mW∕cm2), distinct from cells filled with CuPC derivatives with alkyl chains attached to the core. It is concluded that a critical issue for efficient photocarrier generation is the distance between the CuPC core and the PSi surface. Both organic and inorganic components contribute to photoinduced charge transfer and transport processes. The influence of the PSi structure and pore filling on the solar cell performance is discussed.