The tris(2-pyridyl)phosphine oxide (Py₃PO) complex [Ru(Py₃PO)(bpy)(OH₂)]²⁺ (bpy is 2,2′-bipyridine) is a pH-dependent water oxidation electrocatalyst that accelerates dramatically with increasing pH—up to 780 s⁻¹ at pH 10 (∼1 V overpotential). Despite retaining the pentakis(pyridine) ligand arrangement common to previously reported catalysts, the tripodal Py₃PO ligand framework supports much faster electrocatalysis. The early stages of the catalytic cycle are proposed to follow the typical pattern of single-site ruthenium catalysts, with two sequential 1H⁺/1e⁻ proton-coupled electron transfer (PCET) oxidations, but the pH-dependent onset of catalysis and rapid rates are distinguishing features of the present system.