The design and facile fabrication of highly efficient, cost-effective and earth abundant counter electrode material on an electrode surface is highly desirable for the application of dye-sensitized solar cells (DSSCs). Herein, using a N, N-dimethylformamide based solution process, transition metal chalcogenide NixSy films have been obtained by spin-coating a NiCl2-thiourea (Ni-Tu) solution combining mild thermal treatment. XRD, SEM and TEM characterizations reveal that the current procedure allows for phase composition (Ni3S2, NiS and NiS-NiS2), crystallinity, morphology (film uniformity and compactness) control of the films through simple adjusting Ni/S ratio in the precursor solution. Electrochemical analysis indicates that the FTO supported Ni3S2 and NiS films exhibit excellent electrocatalytic activity toward the reduction of triiodide, resulting in higher photo-electric conversion efficiencies of 6.86% and 6.95% when used as counter electrode in DSSCs, versus 6.66% for Pt. In particular, even without the support of conductive FTO layer, Hall effect measurements and electrocatalytic analysis reveal that pristine NixSy films exhibit good electrical conductivity and electrocatalytic activity, yielding a highest photo-electric conversion efficiency of 4.41% when used as counter electrode in DSSCs. Our study thus provides a facile procedure which allows for composition, morphology optimization and high performance for low-cost, large-scale DSSC application. (C) 2017 Elsevier Ltd. All rights reserved.