Methanol-water reforming is a promising solution for H production/transportation in stationary and mobile hydrogen applications. Developing inexpensive catalysts with sufficiently high activity, selectivity, and stability remains challenging. In this paper, nickel-supported over face-centered cubic (fcc) phase α-MoC has been discovered to exhibit extraordinary hydrogen production activity in the aqueous-phase methanol reforming reaction. Under optimized condition, the hydrogen production rate of 2% Ni/α-MoC is about 6 times higher than that of conventional noble metal 2% Pt/Al O catalyst. We demonstrate that Ni is atomically dispersed over α-MoC via carbon bridge bonds, forming a Ni -C motif on the carbide surface. Such Ni -C motifs can effectively stabilize the isolated Ni sites over the α-MoC substrate, rendering maximized active site density and high structural stability. In addition, the synergy between Ni -C motif and α-MoC produces an active interfacial structure for water dissociation, methanol activation, and successive reforming processes with compatible activity.