Cu2SnS3 (CTS) thin films have been successfully deposited on a cost-effective stainless steel substrate by simple and inexpensive chemical bath deposition (CBD) method. The films are deliberated in provisos of their structural, morphological, optical and photoelectrochemical (PEC) properties before and after annealing treatment, using various physico-chemical techniques. The XRD studies showed the formation of triclinic phase of CTS films with nanocrystalline structure. Also, the crystallinity is enhanced with annealing and the secondary phase of Cu2S observed. Raman analysis confirmed the formation of CTS compound with secondary Cu2S phase. The SEM images also discovered mostly tiny spherical grains and significant progress in the size of grains after annealing. The films possess direct transitions with band gap energies of 1.35 eV and 1.31 eV before and after annealing, respectively. The improved photo-conversion efficiency of CTS thin film based PEC cell is explained with the help of theoretical modeling of energy band diagram and correspondent circuit model of the impedance spectra. (C) 2017 Elsevier Inc. All rights reserved.