Amorphous catalysts possess substantially better catalytic activity toward water splitting than their crystalline counterparts. However, researchers have thus far focused on the crystalline rather than the amorphous phase due to the complexity of synthesis and characterization. Here, crystalline-to-amorphous transformation and charge redistribution induced by Fe and F double substitution on 3D Ni(OH) 2 ultrathin nanosheet arrays are reported as a highly active and stable bifunctional electrocatalyst for urea-assisted water electrolysis. It is unveiled that the synergistic effect of F and Fe dopant incorporation not only alters the electronic configuration for improved intrinsic activity but also creates abundant active sites rich in Ni 3+ , which are responsible for significantly accelerated reaction kinetics. First, our findings show that the collected F−Fe−Ni(OH) 2 catalyst exhibits excellent urea oxidation reaction (UOR) activity with an overpotential of 1.42 V to generate 250 mA cm −2 . Then, the as-prepared catalyst can play a dual role in a whole cell test, presenting a cell voltage of 1.68 V, which is 140 mV lower than that in the overall water-splitting system at 200 mA cm −2 . This work contributes a novel approach to synthesizing Ni-based materials for bifunctional electrocatalysts with enhancement of the catalytic activities of the UOR and the hydrogen evolution reaction.