The B-F codoped nano-TiO2 powders were prepared by the sol-gel method. The surface of powders was modified by stearic acid. The visible light photodegradable PVC/B-F codoped nano-TiO2 composite films were prepared by tape casting processing. Solid-phase visible light photocatalytic degradation of the films were investigated with a 1000W xenon lamp and a ZJB 420 filter glass was used to cut off light of wavelength <420 nm. The weight-loss measurement, SEM, DSC of films were detected. Results showed that the weight loss of PVC/B-F codoped nano-TiO2 composite film (2%TiO2 w/w) is 16.9% after 120h UV irradiation, which is notably higher than that of both the pure PVC film and the PVC/nano-TiO2 composite film. Glass transition (Tg) is appeared for samples after 72h irradiation, and the Tg of PVC/B-F codoped nano-TiO2 composite film is the lowest of all samples. The surface of PVC/B-F codoped nano-TiO2 composite film was destroyed obviously by SEM photo.