The highly anticipated artificial conversion of water to oxygen for the imperishable growth of renewable energy requires efficient water oxidation catalysts (WOCs) to drive the exciting 4e − transformation at low driving potentials. Herein, we describe the freestanding thin film of P 5 Q 7 (TFPQ), where Preyssler [P 5 W 30 O 110 ] 14− (P 5 ) clusters are woven with [CH 3 (CH 2 ) 6 ] 4 N(Br) chains (Q 7 ) to confine P 5 clusters and maximize its catalytic exposure. The TFPQ-supported electrode shows OER at record-low overpotentials at 10 mAcm 2 (η 10 = 130 and 490 mV), rapid migration of electrons (Tafel, 35 and 56 mVdec −1 ), turnover frequency (TOF, 8.55 s −1 ), in alkaline water (1 M KOH), and natural seawater, respectively. Evenly dispersed and confined conducting P 5 clusters with a delocalized charge cloud shows ∼3 times lower η 10 and eventually high OER efficiency than nonconfined clusters. The TFPQ electrodes showed a prolonged stability of minimum 1000 cycles in alkaline water and seawater, without the leaching of true catalytic species P 5 .

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