Water electrolysis suffers from electron transfer barriers during oxygen evolution reactions, which are spin-related for magnetic materials. Here, the electron transfer at the Fe_{64}Ni_{36}-FeNiO_{x}H_{y} interface is effectively accelerated when the electrode is heated to trigger the Invar effect in Fe_{64}Ni_{36} Invar alloy, providing more unoccupied orbitals as electron transfer channels without pairing energy. As a result of thermally stimulated changes in electronic states, Fe_{64}Ni_{36}/FeNiO_{x}H_{y} achieved a cascaded oxidation of the catalytic center and water. Unlike direct modifications made by varying compositions and synthesis, regulating electronic states by energy field opens a new avenue to discover materials with energy coupling effects.