An electrode based on hollow MoS2 spheres intercalated graphene film was firstly fabricated. When used as an electrode in a supercapacitor, the unique structure can provide electrically conducting channels to promote electrolyte penetration and utilize their surface as much as possible. Thus, the resultant binder-free electrode demonstrated a high specific capacity of 286.8[Formula: see text]F[Formula: see text]g[Formula: see text] more than 2 times of pure MoS2 hollow spheres (116.4[Formula: see text]F[Formula: see text]g[Formula: see text]. A supercapacitor based on MoS2/grapheme and active carbon can achieve a maximum energy density of 22.0[Formula: see text]W h[Formula: see text]kg[Formula: see text] at 800[Formula: see text]W[Formula: see text]kg[Formula: see text]. The outstanding electrochemical properties of the hybrid electrode demonstrate that it holds great potential for the next-generation energy storage applications.