Two-dimensional transition metal chalcogenide is a promising non-precious metal electrocatalyst for hydrogen evolution reaction (HER); however, the improvement of an inefficient catalytic activity is still a major challenge at present due to their limited active sites and low conductivity. In this work, we present ultrathin MoSe2 nanosheets were coated on hollow carbon spheres (HCS) surface through strong interaction with surface hydrophilic functional groups OH to fabricate a core-shell HCS@MoSe2 hybrid catalyst. The MoSe2 structure with nanosheets could effectively expose more active edges and the HCS core further provides a beneficial conductivity. Finally, the obtained composite shows the remarkable HER activity with a small Tafel slope of 74 mV dec-1, a small overpotential of 200 mV at a current density of 10 mA cm-2, and an excellent long-term durability. Therefore, this Pt-free and highly efficient electrocatalyst shows its great potential for renewable hydrogen production.