Mismatched electron and proton transport rates impede the manifestation of effective performance of the electrocatalytic oxygen evolution reaction (OER), thereby limiting its industrial applications. Inspired by the natural protein cluster in PS-II, different organic-inorganic hybrid electrocatalysts were synthesized via a hydrothermal method. p-Toluidine (PT), benzoic acid (BA), and p-aminobenzoic acid (PABA) were successfully intercalated into NiFe-LDH. Compared to the organic molecules containing a single functional group, the coexistence of carboxyl and amino groups served as the electron acceptor and donor, respectively, thereby optimizing the electronic structure and suppressing metal dissolution. The overpotential of the PABA-modified catalyst (NiFe-LDH-PABA) was significantly reduced to 225 mV at 10 mA cm-2, and the Tafel slope was only 38.7 mV dec-1. At a high current density of 500 mA cm-2, the NiFe-LDH-PABA catalyst can work stably in a 1 M KOH solution at 25 °C over 550 h with 96% retention of its initial activity. Density functional theory (DFT) calculations further confirmed that the work offers significant insight into the modulation by organic molecular structure and provides a new paradigm for creating organic-inorganic hybrid OER catalysts.