Sol-gel method was used to prepare polyvinyl alcohol/titanium dioxide (PVA/TiO2) composite films on glass slide, then the heat-treated polyvinyl alcohol/titanium dioxide (H-PVA/TiO2) composite loaded on glass and used as photo-catalyst was prepared by calcinating the precursor. Scanning electron microscopy (SEM), X-ray diffractionscopy (XRD), ultraviolet-visible diffuse reflection spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (RAM) and fluorescence emission spectroscopy (FL) were used to characterize H-PVA/TiO2 composites. The visible light-induced photo-catalytic activities of the obtained composites prepared by different heat-treated temperature and different composition were examined through investigating the decolouration of rhodamine B (RhB) solution under visible light irradiation in the presence of the composites by means of UV-vis measurement. The results show that under the visible light irradiation, the H-PVA/TiO2 composite can make rhodamine B be degraded more efficiently than the PVA/TiO2 composite does, and the visible light photo-catalytic activity obviously depends on the heat-treated temperature and the composite composition. The 180 degrees C of heat-treated temperature and the 16.7 mass% of polymer content are beneficial for enhancing the efficiency of H-PVA/TiO2 of degrading RhB. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.