Ruthenium-doped amorphous molybdenum dioxide coupled with a reduced graphene oxide hybrid (Ru-MoO2@PC/rGO) is synthesized using polyoxometalate-based MOFs/GO as a precursor. Benefitting from the synergistic effect of numerous exposed active sites, Ru dopants and the introduction of GO, the designed catalyst shows exceptional electrocatalytic performance toward the HER in alkaline media.