The ZnFe2O4 and TiO2 nanocomposite films was prepared by Sol-Gel method on conductive glass, and the influence factors of it’s photoelectrocatalytic performence such as the film layer, pole and voltage was investigated. The results indicated that: the photocatalytic effects of composite films with ZnFe2O4+ TiO2+ ZnFe2O4 was the best. The decomposing ratio of methyl orange with the photoelectrocatalysis of composite films at voltage 0.2-6V all increased unstably.At the same time, the distance from films to pole plank also had the effects on the photocatalytic activities of the films.