In order to construct the molybdenum disulfide (MoS2) hybrid nanostructure with enhanced conductivity and more active sites towards electrocatalytic hydrogen evolution reaction (HER), hierarchical P-doped MoS2 nanopetals decorated N-doped hollow carbon spheres (N-C@P-MoS2) core-shell structures were synthesized via calcination and hydrothermal methods. N-C@P-MoS2 with optimized loadings exhibited favorable HER activities with low onset overpotential (117 mV), small Tafel slopes (68 mV/dec), and fine stability compared with pure MoS2 nanosheets and all undoped samples. This is largely ascribed to the synergy of MoS2 and carbon in the rational hierarchical structures, as well as the modified electronic structure with improved conductivity, increased active sites by virtue of N and P doping. Furthermore, P-doped MoS2 nanosheets were encapsulated in carbon spheres (N-C/P-MoS2 (inside)) by controlling the dropping rate of adding MoS2 precursors. As the active sites were hampered, the N-C/P-MoS2 (inside) revealed poor HER performance compared with the core-shell counterparts. The results demonstrate that the fabrication of hierarchical MoS2/carbon composites with the synergy of structural (morphology and content) and electronic (active sites and conductivity) effects induced by various nonmetal doping pave the way for enhanced electrocatalytic HER activities. (C) 2018 Elsevier Ltd. All rights reserved.