Addressed herein is the superior catalytic performance of reduced graphene oxide supported Ni30Pd70 alloy nanoparticles (rGO–Ni30Pd70) for the direct hydrogenation of alkenes and alkynes to alkanes, which surpasses the commercial Pd/C catalyst both in activity and stability. A variety of cyclic or aromatic alkenes and alkynes (a total of 17 examples) were rapidly reduced to the corresponding alkanes with high yields (>99%) via the presented direct hydrogenation protocol under ambient conditions. Compared to the commercially available Pd/C (10 wt%) catalyst, the rGO–Ni30Pd70 catalyst provided higher yields in shorter reaction times under the optimized conditions. Moreover, the rGO–Ni30Pd70 catalysts were more stable and durable than the commercial Pd/C catalysts by preserving their initial activity after five consecutive runs in the hydrogenation reactions.