Organic ligands in metal-organic frameworks (MOFs) play an indispensable role in the reconstruction and catalysis during the alkaline oxygen evolution reaction (OER). However, it is still a big challenge to maintain a high content of ligands in MOF-reconstructed OER electrocatalysts and to study the interaction between ligands and derived (oxy)hydroxides. Herein, a ligand-rich trimetallic amorphous electrocatalyst is fabricated through a two-step mechanochemical and electrochemical reconstruction strategy. Experimental and theoretical studies clearly reveal that the d-π interaction between delocalized π-electrons on the benzene ring of ligands and derived (oxy)hydroxides, can trigger the charge transfer from ligands to the active metal centers, thus optimizing the adsorption energy of the oxygen-containing intermediates and enhancing the OER performance. Moreover, an anion-exchange membrane water electrolyzer using such ligand-rich OER electrocatalyst can be operated steadily at 1.69 V and 55 °C under an industrial-level current density of 500 mA cm^-2 for over 200 h. This work provides novel insights into the role of organic ligands in alkaline OER electrocatalysis, with the potential to facilitate the production of green hydrogen at industrial-level current densities.