A novel cotton shells-like composite of uniform MoS2 with the carbon coated is prepared by a simple and efficient route. This particular MoS2@C hybrid is beneficial for a dye-sensitized solar cell (DSSC) as an inexpensive but high efficient platinum-free counter electrode. Meanwhile, the synergistic effects of catalytically active MoS2 flower-morphology and conductive carbon supports are conducive to improve charge transfer resistance, electrocatalytic activity and fast reaction kinetics of the reduction of triiodide. The DSSC assembled with this original MoS2@C counter electrode (CE) indicates superior photoelectric conversion efficiency (6.93%), which exceeds that of the DSSC with a Pt counter electrode (6.68%).