A magnesiothermic reduction route has been presented to synthesize phase-pure germanides that are not readily available traditionally. The obtained ruthenium germanide (RuGe) serves as an efficient non-Pt electrocatalyst for hydrogen evolution, and its intrinsic activity is very close to that of Pt. Our combined theoretical and experimental study demonstrates that the remarkable performance is derived from the germanium-induced change in hydrogen site preference from hollow to efficient Ru top sites.