Nanocrystalline CaFe2O4 oxide semiconductor with spinel structure was synthesized by polymerized complex (PC) method and investigated for its physical and optical properties. The crystallization of CaFe2O4 made by PC method was found to occur in the temperature range of 700-1100 degrees C. The observation of highly pure phase and such lower crystallization tempearture in CaFe2O4 made by PC method, is in total contrast to that observed in CaFe2O4 prepared by the conventional solid-state reaction (SSR) method. The activation energy required for the growth of nanocrystalline CaFe2O4 in PC sample was found to be 8.4 kJ/mol. The band gap of nanocrystalline CaFe2O4 determined by UV-DRS was 1.91 eV (647 nm). The photocatalytic activity of PC materials for iso-propyl alcohol photodegradation under visible light (> or =420 nm) was much higher than that of SSR materials.