Layered hydroxides have shown superior catalytic activity for the electrocatalytic organic compound oxidation reaction. However, metal leaching can lead to uncontrollable structural phase transformation. Here, we report a Cr-Ni(OH) 2 electrocatalyst as a model of a pre-catalyst for the identification of the structure-performance relationship. The optimized electrocatalyst delivered superb performances, i.e., a low potential of 1.38 V (versus reversible hydrogen electrode [RHE]) to reach 100 mA cm −2 and stable activity over 200 h at 10 mA cm −2 . In situ analyses and theoretical calculations demonstrate that well-tuned electronic structures and the superhydrophilic-superaerophobic surface can enable rapid urea oxidation reaction (UOR) kinetics, which reduces the specific adsorption OH − and significantly depresses Cr dopants leaching, and this helps to maintain high UOR performance. Furthermore, the crucial role of mass transfer improvement to alleviate the structural decay under high potentials is disclosed. • Catalyst with suitable wettability and optimized electronic structures was achieved • Rapid UOR kinetics significantly suppress Cr leaching • The improvement in mass transfer is crucial in stabilizing efficient structures The electrocatalytic organic compound oxidation reaction has been extensively employed to replace water electro-oxidation. However, most of their electrocatalysts suffer from sluggish kinetics with a large overpotential, further resulting in uncontrollable structural reconstruction of the catalyst. Here, a Cr-Ni(OH) 2 electrocatalyst with well-controlled superhydrophilicity-superaerophobicity was developed as a model to understand the structural stability of metal hydroxides during alkaline urea oxidation reaction (UOR). The rapid UOR kinetics of the Cr-Ni(OH) 2 electrocatalysts can ensure the high stability of efficient structures, resulting in best-in-class performances. Importantly, the discovery of structure and phase transformation at high potentials due to mass transfer limits created optimal electrocatalyst conditions for Cr-Ni(OH) 2 to promote urea-assisted hydrogen production, which is generally ignored by the field. A robust structure of electrocatalysts is critical for achieving a highly efficient urea oxidation reaction. Here, we demonstrate the regulation of electronic structures and the superwetting property of electrocatalysts in obtaining rapid UOR kinetics. Corroborated with in situ spectrum studies and theoretical calculations, rapid UOR kinetics can significantly suppress Cr dopants leaching, and mass transfer improvement plays a key role in stabilizing efficient structures at high potential.