An effieient hybrid counter electrode (CE) of CuMnSnS4 (CMTS)/carbon nanotubes (CMTS/CNTs) was prepared by using an in situ solvothermal route, and the dye-sensitized solar cells (DSSCs) based on the CMTS/CNTs CE contained 0.05 g CNTs exhibited an improved power conversion efficiency of 8.97% under illumination of 100 mw.cm(-2). The crystal structure, elemental composition and morphology of samples were characterised by using XRD, EDS, TEM and SEM, and we found that the CMTS nanoflowers have no changing with and without polyvinylpyrrolidone particioation except the larger particle size for the latter. The CNTs distributed uniformly in the CMTS nanoflowers and formed a new microsphere. The extensive electrichemical characterizations including cyclic voltammetry, electrochemical impedance and Tafel curves for the CMTS/CNTs were implemented, and it showed better electrocatalytic activity and lower charge transfer resistance at the electrolyte ICE interface for I-/I3- liquid electrolyte compared to the Pt electrode under the optimized condition.