The oxygen evolution reaction (OER), a crucial semireaction in water electrolysis and rechargeable metal−air batteries, is vital for carbon neutrality. Hindered by a slow proton-coupled electron transfer, an efficient catalyst activating the formation of an O−H bond is essential. Here, we proposed a straightforward one-step hydrothermal procedure for fabricating PO 4 3− -modified NiFe layered double-hydroxide (NiFe LDH) catalysts and investigated the role of PO 4 3− anions in enhancing OER. Phosphate amounts can efficiently regulate LDH morphology, crystallinity, composition, and electronic configuration. The optimized sample showed a low overpotential of 267 mV at 10 mA cm −2 . Density functional theory calculations revealed that intercalated and surface-adsorbed PO 4 3− anions in NiFe LDH reduced the Gibbs free energy in the rate-determining step of *OOH formation, balancing oxygen-containing intermediate adsorption/dissociation and promoting the OER. Intercalated phosphate ions accelerated precatalyst dehydrogenation kinetics, leading to a rapid reconstruction into active NiFe oxyhydroxide species. Surface-adsorbed PO 4 3− interacted favorably with adsorbed *OOH on the active Ni sites, stabilizing *OOH. Overall, the synergistic effects of intercalated and surface-adsorbed PO 4 3− anions significantly contributed to enhanced OER activity. Achieving optimal catalytic activity requires a delicate equilibrium between thermodynamic and kinetic factors by meticulously regulating the quantity of introduced PO 4 3− ions. This endeavor will facilitate a deeper comprehension of the influence of anions in electrocatalysis for OER.