MoS2, as a catalyst, has attracted broad attention in recent years due to its high catalytic activity and low cost. However, MoS2 stacks readily, especially the one synthesized by calcination which is close to bulk, so it limits the number of exposed active site. Carbon materials possess excellent electrical conductivity and large surface area. In this paper, N‐doped hollow carbon sphere coated MoS2 (NHCS@MoS2) nanocomposites are synthesized via one‐step calcination treatment of the polypyrrole@(NH4)2MoS4 core shell structure directly. Compared with bare MoS2, the NHCS@MoS2 shows remarkably high electrocatalytic activity for hydrogen evolution with the overpotential of 190 mV to reach the current density of 10 mA cm−2. Both small tafel slope and Rct suggest that NHCS@MoS2 has a high hydrogen dissociation rate. Furthermore, it also exhibits excellent stability.