Developing cheap and abundant materials as high efficient HER catalysts to replace noble metal catalysts is urgent. Molybdenum disulfide (MoS2) as one attention-drawing material still has an enormous limit due to the layers stacking and the lacking of active sites. Therefore, the N, P dual-doped MoS2 on hollow carbon spheres (denoted as P-MoS2@NCs) has been developed via template sacrifice, polymerization, and hydrothermal process. The synergistic effect between the N, P dual-doped hollow carbon spheres, and MoS2, which has abundant active sites can enhance the electrocatalytic performance of HER. As expected, the formed P-MoS2@NCs-2 exhibits excellent electrochemical property for HER. The overpotential at 10 mA cm−2 and Tafel slope are as low as 147 mV (V vs RHE) and 72 mV/dec. Otherwise, it shows excellent durability in 0.5 M H2SO4. It provides a new method to develop advanced MoS2-based catalyst for the HER.