Comparing with the binary chalcogenides, the ternary chalcogenides may achieve higher electrical conductivity and electrochemical activity due to the synergistic effect of the different metal cations. Herein, ternary nickel iron selenide (Ni0.5Fe0.5Se2) was fabricated through a facile one-pot solvothermal method with the assistance of glucose for the first time. The dye-sensitized solar cells (DSSCs) were assembled with the as-prepared Ni0.5Fe0.5Se2 as counter electrode (CE). Electrochemical measurements indicated that the Ni0.5Fe0.5Se2 possessed small electron transfer resistance at the interface between electrode and electrolyte, great electrocatalytic activity and reaction kinetics toward the reduction of triiodide. Compared with conventional pt CE (7.24%), the DSSCs based on Ni0.5Fe0.5Se2 CE achieved a greater power conversion efficiency of 7.89%. Furthermore, this study provides a new idea and strategy with convenient method to synthesize Pt-free alternative materials.