Single-crystalline Cu2ZnSnS4 (CZTS) nanorods with a kesterite crystal phase were synthesized using a facile solvothermal reaction. Thin-film electrodes for p-type CZTS nanorods and n-type metal oxide semiconductor composites were fabricated on mesoporous n-type metal oxide electrodes by introducing the electrodes into a solvothermal condition. The composites exhibited high photocurrent and strong photocatalytic oxidative activity for the decomposition of organic compounds.