A novel dual-site segmentally synergistic catalysis mechanism (DSSM) has been proposed for CoFeSₓ nanoclusters supported on carbon nanotubes (CFS-ACs/CNT) to enhance the oxygen evolution reaction (OER) for sustainable water oxidation. This mechanism effectively breaks the scaling relationship between key oxygen intermediates without sacrificing stability. The Co³⁺ site provides strong OH* adsorption energy, while Fe³⁺ exhibits strong O* adsorption. These dual sites synergistically produce Co-O-O-Fe intermediates, accelerating the release of triplet-state oxygen (↑O=O↑). The CFS-ACs/CNT catalyst exhibits lower overpotential than commercial IrO₂ and demonstrates remarkable stability (633 h without significant potential loss). The development of efficient OER catalysts remains challenging due to the complex multi-step proton-coupling reaction and the destruction of the catalyst surface in strong oxidizing environments. The adsorption evolution mechanism (AEM) and lattice-oxygen-mediated mechanism (LOM) have limitations in balancing high activity and stability. The oxide path mechanism (OPM) allows direct O-O coupling without oxygen vacancies, but requires symmetric bimetallic positions with appropriate atomic distances. The DSSM mechanism, based on the OPM, enables efficient O-O coupling by leveraging the spin state of the metal sites. The CFS-ACs/CNT catalyst, synthesized via a facile adsorption reduction-hydrothermal method, exhibits excellent OER performance with a low overpotential of 270 mV at 20 mA cm⁻² and a small Tafel slope of 77.6 mV·dec⁻¹. The catalyst demonstrates high electrochemical activity and stability, with a 633 h operation without significant potential loss. The spin state of the metal sites plays a crucial role in the OER process, with Co³⁺ (L.S., t₂g⁶e_g⁰) and Fe³⁺ (M.S., t₂g⁴e_g¹) sites contributing to strong OH* and O* adsorption, respectively. The DSSM mechanism enables the simultaneous presence of Co-O* and Fe-O* species, triggering the O-O coupling mechanism and facilitating the formation of the adsorbed Co-O-O-Fe intermediate. DFT calculations further confirm the feasibility of the O-O coupling mechanism, showing a lower energy barrier (1.12 eV) compared to the AEM pathway. The DSSM mechanism offers a promising strategy for achieving high OER activity and stability by leveraging the spin state of the metal sites. The study provides new insights into the impact of spin state changes on oxygen adsorption intermediates during OER and highlights the potential of the DSSM mechanism for sustainable water oxidation.A novel dual-site segmentally synergistic catalysis mechanism (DSSM) has been proposed for CoFeSₓ nanoclusters supported on carbon nanotubes (CFS-ACs/CNT) to enhance the oxygen evolution reaction (OER) for sustainable water oxidation. This mechanism effectively breaks the scaling relationship between key oxygen intermediates without sacrificing stability. The Co³⁺ site provides strong OH* adsorption energy, while Fe³⁺ exhibits strong O* adsorption. These dual sites synergistically produce Co-O-O-Fe intermediates, accelerating the release of triplet-state oxygen (↑O=O↑). The CFS-ACs/CNT catalyst exhibits lower overpotential than commercial IrO₂ and demonstrates remarkable stability (633 h without significant potential loss). The development of efficient OER catalysts remains challenging due to the complex multi-step proton-coupling reaction and the destruction of the catalyst surface in strong oxidizing environments. The adsorption evolution mechanism (AEM) and lattice-oxygen-mediated mechanism (LOM) have limitations in balancing high activity and stability. The oxide path mechanism (OPM) allows direct O-O coupling without oxygen vacancies, but requires symmetric bimetallic positions with appropriate atomic distances. The DSSM mechanism, based on the OPM, enables efficient O-O coupling by leveraging the spin state of the metal sites. The CFS-ACs/CNT catalyst, synthesized via a facile adsorption reduction-hydrothermal method, exhibits excellent OER performance with a low overpotential of 270 mV at 20 mA cm⁻² and a small Tafel slope of 77.6 mV·dec⁻¹. The catalyst demonstrates high electrochemical activity and stability, with a 633 h operation without significant potential loss. The spin state of the metal sites plays a crucial role in the OER process, with Co³⁺ (L.S., t₂g⁶e_g⁰) and Fe³⁺ (M.S., t₂g⁴e_g¹) sites contributing to strong OH* and O* adsorption, respectively. The DSSM mechanism enables the simultaneous presence of Co-O* and Fe-O* species, triggering the O-O coupling mechanism and facilitating the formation of the adsorbed Co-O-O-Fe intermediate. DFT calculations further confirm the feasibility of the O-O coupling mechanism, showing a lower energy barrier (1.12 eV) compared to the AEM pathway. The DSSM mechanism offers a promising strategy for achieving high OER activity and stability by leveraging the spin state of the metal sites. The study provides new insights into the impact of spin state changes on oxygen adsorption intermediates during OER and highlights the potential of the DSSM mechanism for sustainable water oxidation.