In this study, poly (4-vinylphenol) (denoted as PVP) was firstly used as a stable and low-cost sensitizer of titania for visible light photocatalysis. The PVP thin-layer was readily grafted on TiO2 (PVP/TiO2) through surface complexation between the multiple hydroxyl groups of PVP and the surface titanol groups (Ti-OH), via simple dispersion of PVP and TiO2 powders in organic solvent. We have demonstrated that the PVP layer sensitizes TiO2 under visible light through the ligand-to-metal charge transfer (LMCT) mechanism. The PVP/TiO2 (with platinum as co-catalyst) composite exhibited a visible light activity of H-2 production in the presence of suitable electron donors, whereas phenol-complexed TiO2 (compared as a control) did not generate H-2 in the identical condition. Furthermore, PVP/TiO2 exhibited efficient photo catalytic degradation of organic pollutant (4-cholorophenol) under visible light irradiation. In addition, the photoelectrochemical measurements for PVP/TiO2-coated electrodes (PVP/TiO2/FTO) supported the visible light-induced LMCT process on PVP/TiO2, which involves the direct electron transfer from the highest occupied molecular orbital (HOMO) of PVP to the conduction band of TiO2 as the origin of the visible light photocatalytic activity. (C) 2016 Elsevier B.V. All rights reserved.