Heterogeneous dual‐site electrocatalysts are emerging cutting‐edge materials for efficient electrochemical water splitting. However, the corresponding oxygen evolution reaction (OER) mechanism on these materials is still unclear. Herein, based on a series of in‐situ spectroscopy experiments and density function theory (DFT) calculations, a new heterogeneous dual‐site O‐O bridging mechanism (DSBM) is proposed. This mechanism is to elucidate the sequential appearance of dual active sites through in‐situ construction (hybrid ions undergo reconstruction initially), determine the crucial role of hybrid dual sites in this mechanism (with Ni sites preferentially adsorbing hydroxyls for catalysis followed by proton removal at Fe sites), assess the impact of O‐O bond formation on the activation state of water (inducing orderliness of activated water), and investigate the universality (with Co doping in Ni(P4O11)). Under the guidance of this mechanism, with Fe‐Ni(P4O11) as pre‐catalyst, the in‐situ formed Fe‐Ni(OH)2 electrocatalyst has reached a record‐low overpotential of 156.4 mV at current density of 18.0 mA cm‐2. Successfully constructed Fe‐Ni(P4O11)/Ti uplifting the overall efficacy of the phosphate from moderate to superior, positioning it as an innovative and highly proficient electrocatalyst for OER.