A series of carbon black-supported bimetallic Ru–Co nanoparticles catalyst were synthesized via the chemical reduction of corresponding metal precursor in ethylene glycol, for H2 generation from NaBH4 methanolysis. The composition, morphology and structure of the novel nanomaterial were well characterized by XRD, XPS, HRTEM, EDX and SEM, showing the good dispersion of supported Ru–Co nanoparticles with an average diameter of 2.4 nm. Significantly, the highest H2 generation rate is observed in the case of Ru–Co/C catalyst with Ru/Co ratio of 5, achieving 9.36 L min−1 g−1 at 25 °C, which is comparable to the reported pure Ru catalysts. Furthermore, the recycle test confirms our catalyst can be practically applied. Our work highlights the synergetic effect in bimetallic catalytic system for boosting H2 generation rates from NaBH4 methanolysis.