Direct methanol fuel cell (DMFC) is hampered by the sluggish methanol oxidation reaction. In this work, we have invited rhodium phosphides (Rh 2 P) to platinum (Pt) as robust MOR electrocatalyst ascribing the excellent water dissociation capability of Rh 2 P to generate Pt(OH) ads species to mitigate the CO poisoning. MOR mass activity of Rh 2 P-Pt/C is enhanced by 2- and 3.5-time with relative to commercial Pt/C and PtRu/C, respectively; additionally, the CO anti-poisoning ability is also boosted by 2.4 folds than Pt/C. The in-situ electrochemical impedance spectroscopy test reveals that the water dissociation is accelerated by Rh 2 P; moreover, the mutual electronic interplay between Pt and Rh 2 P contributes to a superior resistance towards electrochemical dissolution and coalescence. The theoretical investigation also indicates that d band center of Pt in Rh 2 P-Pt is downshifted resulting in a lower CO binding strength.