Cobaltosic sulfide (Co3S4) was synthesized by hydrothermal synthesis method. Combining the ball grinding mill and spray method. Co3S4 was prepared into counter electrode (CE) and fabricated dye-sensitized solar cells (DSCs) with the novel electrolyte Co2+/Ce3+. The power conversion efficiency (PCE) obtained by the DSCs based on the pure Co3S4 CE was only 6.06%. which was much smaller than that of Pt (8.05%). To improve the catalytic activity of pure Co3S4, electrospun carbon nanofibers (ECs) were fabricated by the electrospun method and the composite of ECs supported cobahosic sulfide (Co3S.JECs) was synthesized by hydrothermal synthesis method. And the DSCs based on Co3S4/ECs CE achieved a high PCE of (8.22 0.08)%, which was a little higher than that of Pt (8.05%).