Structural phase transition offers an effective means to modulate interfacial electronic states and accelerate electron transfer in water electrolysis. Here, we exploit a heat-induced monoclinic-to-tetragonal phase transition in ${\mathrm{VO}}_2$ to facilitate electron transfer at ${\mathrm{VO}}_2/{\mathrm{MO}}_{\mathrm{x}}{\mathrm{H}}_{\mathrm{y}}(\mathrm{M}=\mathrm{Co},\mathrm{Ni},\mathrm{Fe})$ heterojunction interfaces. The thermally triggered electronic restructuring lowers the Fermi level of ${\mathrm{VO}}_2$ relative to ${\mathrm{MO}}_{\mathrm{x}}{\mathrm{H}}_{\mathrm{y}}$, promoting the formation of high-valence active species. This significantly accelerates oxygen evolution reaction (OER) kinetics, driving a cascade of catalytic center activation and water oxidation. Our Letter establishes that coupling active catalysts with controllable phase transitions represents a viable strategy for synergistic heat-electricity activation in OER catalysis.

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• Electrochemical properties
• Phase transitions
• First-principles calculations