In present investigation, Cu2ZnSnS4(CZTS) thin films have been deposited on to glass substrates by novel chemical successive ionic layer adsorption and reaction (SILAR) method. The effect of air annealing in the temperature range between 573 and 773 K on the structural, morphological, optical and electrical properties has been studied. The X-ray diffraction studies revealed the formation of polycrystalline CZTS films. The surface morphological study showed smooth, compact and uniform film formation after annealing formation. The band gap was in between range from 1.5 to 1.8 eV depending on annealing temperature. The thermo emf measurement revealed that the CZTS exhibits p-type electrical conductivity. Further, photoactivity of CZTS thin films was tested by forming the photoelectrochemical cell. (C) 2012 Elsevier Ltd. All rights reserved.