Molybdenum-based compounds show promising promotion effects on Pt catalysts for energy-relevant catalysis reactions. Herein, a more effective promotion effect of MoP than MoC was found in assisting Pt nanoparticles for methanol-assisted hydrogen generation in light of the strong metal-support interaction and synergistic effect between Pt and MoP/C nanospheres. Electrochemical analyses and theoretical calculations demonstrated that Pt-MoP/C facilitated the oxidation and removal of CO intermediates more effectively than Pt-MoC/C. This enhanced performance was attributed to the distinct 6-coordination environment of hexagonal MoP and the elevated electron density of Mo induced by phosphorus. These structural and electronic features significantly enhanced electron transfer to Pt, thereby creating strong metal-support interaction and synergistic effect to improve the overall catalytic efficiency. Especially, the unique activities of Mo