Molybdenum disulfide, as an electronic highly-adjustable catalysts material, tuning its electronic structure is crucial to enhance its intrinsic hydrogen evolution reaction (HER) activity. Nevertheless, there are yet huge challenges to the understanding and regulation of the surface electronic structure of molybdenum disulfide-based catalysts. Here we address these challenges by tuning its electronic structure of phase modulation synergistic with interfacial chemistry and defects from phosphorus or sulfur implantation, and we then successfully design and synthesize electrocatalysts with the multi-heterojunction interfaces (e.g., 1T0.81-MoS2@Ni2P), demonstrating superior HER activities and good stabilities with a small overpotentials of 38.9 and 95 mV at 10 mA/cm2, a low Tafel slopes of 41 and 42 mV/dec in acidic as well as alkaline surroundings, outperforming commercial Pt/C catalyst and other reported Mo-based catalysts. Theoretical calculation verified that the incorporation of metallic-phase and intrinsic HER-active Ni-based materials into molybdenum disulfide could effectively regulate its electronic structure for making the bandgap narrower. Additionally, X-ray absorption spectroscopy indicate that reduced nickel possesses empty orbitals, which is helpful for additional H binding ability. All these factors can decrease Mo-H bond strength, greatly improving the HER catalytic activity of these materials.