Kesterite-structure Cu2ZnSnSe4 (CZTSe) has been recommended to be a promising Pt-free counter electrode (CE) candidate for dye-sensitized solar cells (DSSCs), owing to its excellent catalytic activity, hierarchical microstructure, and natural abundance. Herein, based on a facile electrodeposition method and mild solvothermal treatment, we prepared great crystallinity CZTSe nanostructure on FTO substrate as DSSCs cathode directly, demonstrating a satisfied power conversion efficiency of 7.56% and a relatively long-operation life performance. The impressive performance was ascribed from the CZTSe thin film good adhering to conductive substrate, high catalytic activity, effective photo-generated electron migration, and low charge transfer resistance at the interface of the catalytic material and substrate. Our present results prove that the CZTSe nanostructure is a promising and effective Pt-free counter cathode in dye-sensitized solar cells. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.