Abstract Developing novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy‐saving hydrogen production. Herein, we report an ambient and controllable γ‐ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect‐rich manganese oxides (M@MnO 2‐x , M=Ru, Pt, Pd, Ir) for glycerol‐assisted H 2 evolution. Benefiting from the strong penetrability of γ‐rays, nanoparticles and defect supports are formed simultaneously and bridged by metal‐oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru−O−Mn bonds activate the Ru and Mn sites in Ru@MnO 2‐x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm −2 in a continuous‐flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO 2‐x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect‐rich MnO 2 support promotes the dissociation of H 2 O, while the defect‐regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol‐assisted hydrogen production.