In this study, calcium ferrite (CaFe2O4) nanorod thin films are synthesized using the molten salt method and applied to photocathodes. SEM observation showed nanorod structure was constructed on Pt substrate by this method with lower temperature than conventional processes. Moreover, photoelectrochemical results demonstrate that the synthesized CaFe2O4 nanorods exhibited higher photo response as compared to CaFe2O4 rods prepared without using this method. Thus, the method in this work provides an economical avenue for facile synthesis of CaFe2O4-based photofunctional materials.