Urea, a prevalent component found in wastewater, shows great promise as an alternative substrate to water for energy-efficient hydrogen production by electrolysis. However, the sluggish kinetics of the anodic urea oxidation reaction (UOR) significantly hampers the overall reaction rate. To address this challenge, this article presents a comprehensive study focusing on the controlled fabrication of hierarchically structured nanomaterials as potential catalysts for UOR. The prepared MnO2@NiCo-LDH hybrid catalyst demonstrates remarkable improvements in reaction kinetics, benefiting from synergistic enhancements in charge transfer and efficient mass transport facilitated by its unique three-dimensional architecture. Notably, the catalyst exhibits an exceptionally low onset potential of 1.228 V and requires only 1.326 V to achieve an impressive current density of 100 mA cm-2, representing a state-of-the-art performance in UOR. These findings highlight the tremendous potential of this innovative material-designing strategy to drive advancements in electrocatalytic processes.