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.

High‐precision separation with increased water permeability is critical for efficient membrane‐based water treatment processes. To achieve high selectivity toward different targeted species while allowing rapid water transportation, the structure of the membrane polyamide selective layer requires delicate regulation. Herein, an effective approach to systematically expand the pore size of polyamide layers by incorporating ammonium ion‐modified carbon dots (CDs) into the polyamide network is developed. The ammonium ions with different alkyl chain lengths attached to the CDs create nanochannels of different sizes in the network to lower the energy barrier for water transportation while maintaining high selectivity to targeted species. When the alkyl chain length of the ammonium ions reaches eight carbon atoms (i.e., C₈ ions), the amphiphilic C₈‐CDs induce the formation of the ridged nanostructure on the membrane surface and hence the increased membrane filtration area. The resultant thin‐film nanocomposite (TFN) membrane, denoted as the TFN‐C₈‐CDs membrane, demonstrates a higher Na₂SO₄ rejection of 98.9% and NaCl/Na₂SO₄ selectivity of 83.1 than the pristine polyamide membrane, together with a tripled pure water permeability of 29.0 L m⁻² h⁻¹ bar⁻¹. Herein, a viable approach for ingeniously designing the nanochannels and surface nanostructure of polyamide membranes for more efficient filtration processes is provided.