Molybdenum disulfide (MoS2) is considered as a promising candidate to Pt-based catalysts. Literatures report the active centers of MoS2 locate at its edges, while the perfect in-plane domains are not active. In this study, a simple Co-Mo-S precursor decomposition approach is used to synthesize Co-doped MoS2 in-situ grown graphite paper (GP) substrate. Electrochemical analyses reveal the Co-doped MoS2 possesses excellent electrocatalytic activity comparable to Pt. Density functional theory (DFT) calculations indicate the inert in-plane S atoms neighboring the doped Co atoms become active towards triiodide reduction, as revealed by the adsorption energies (E-ad) of iodine atom decreasing from 0.36 eV to -0.52 eV, identical with value obtained from Pt (-0.52 eV). Due to increased active sites, highly conductive of GP, and excellent electrical connection between Co-doped MoS2 and GP substrate, the dye-sensitized solar cell fabricated using Co-doped MoS2/GP as counter electrode (CE) shows higher photoelectric conversion efficiency (7.26%) than those based on MoS2/GP CE (6.57%) and platinized F-doped tin oxide (Pt/FTO) electrode (6.87%). (c) 2018 Published by Elsevier Ltd.