Tuning the local environment of nanomaterial-based catalysts has emerged as an effective approach to optimize their oxygen evolution reaction (OER) performance, yet the controlled electronic modulation around surface active sites remains a great challenge. Herein, directed electronic modulation of NiO nanoparticles was achieved by simple surface molecular modification with small organic molecules. By adjusting the electronic properties of modifying molecules, the local electronic structure was rationally tailored and a close electronic structure-activity relationship was discovered: the increasing electron-withdrawing modification readily decreased the electron density around surface Ni sites, accelerating the reaction kinetics and improving OER activity, and vice versa. Detailed investigation by operando Raman spectroelectrochemistry revealed that the electron-withdrawing modification facilitates the charge-transfer kinetics, stimulates the catalyst reconstruction, and promotes abundant high-valent gamma-NiOOH reactive species generation. The NiO-C(6)F(5)catalyst, with the optimized electronic environment, exhibited superior performance towards water oxidation. This work provides a well-designed and effective approach for heterogeneous catalyst fabrication under the molecular level.