Improving the catalytic efficiency of platinum for the hydrogen evolution reaction is valuable for water splitting technologies. Hydrogen spillover has emerged as a new strategy in designing binary-component Pt/support electrocatalysts. However, such binary catalysts often suffer from a long reaction pathway, undesirable interfacial barrier, and complicated synthetic processes. Here we report a single-phase complex oxide La₂Sr₂PtO_7+δ as a high-performance hydrogen evolution electrocatalyst in acidic media utilizing an atomic-scale hydrogen spillover effect between multifunctional catalytic sites. With insights from comprehensive experiments and theoretical calculations, the overall hydrogen evolution pathway proceeds along three steps: fast proton adsorption on O site, facile hydrogen migration from O site to Pt site via thermoneutral La-Pt bridge site serving as the mediator, and favorable H₂ desorption on Pt site. Benefiting from this catalytic process, the resulting La₂Sr₂PtO_7+δ exhibits a low overpotential of 13 mV at 10 mA cm⁻², a small Tafel slope of 22 mV dec⁻¹, an enhanced intrinsic activity, and a greater durability than commercial Pt black catalyst.