A novel ultrathin-walled Co9S8 nanotube/reduced graphene oxide electrocatalyst, for the first time, is successfully prepared by a simple hydrothermal process coupling with an ion exchange process for the reduction of triiodide in dye-sensitized solar cells (DSSC). Ultrathin-walled Co9S8 nanotubes have an average diameter of 20-30 nm and a wall thickness of 3-4 nm, and the reduced graphene oxide possessing high conductivity is well dispersed in the Co9S8 nanotubes simultaneously, which contributed to the high specific surface area, well exposed active sites and excellent electric conductivity. The electrochemical performances of ultrathin-walled Co9S8 nanotube/reduced graphene oxide are evaluated by the EIS, Tafel polarization and CV measurements, exhibiting the significant improvement of electrocatalytic performance for the triiodide reduction. Optimizing the film thickness of Co9S8 nanotube/reduced graphene oxide counter electrode, the optimum photovoltaic conversion efficiency of 7.58% is obtained, which is even higher than that of the DSSC with Pt counter electrode (7.45%). In addition, the DSSC with Co9S8/reduced graphene oxide electrode exhibits a good repeatability and long-term electrochemical stability. Therefore, the ultrathin-walled Co9S8 nanotube/reduced graphene oxide is a reliable material to replace Pt. (C) 2016 Elsevier B.V. All rights reserved.