The electrocatalytic urea oxidation reaction (UOR) has attracted substantial research interests over the past few years owing to its critical role in coupled electrochemical systems for energy conversion, for example, coupling with the hydrogen evolution reaction (HER) to realize urea-assisted hydrogen production and assembling direct urea fuel cells (DUFC) by coupling with the oxygen reduction reaction (ORR). The UOR process has been proved to be a two-step process which involves an electrochemical pre-oxidation reaction of the metal sites and a subsequent chemical oxidation of the urea molecules on the as-formed high-valence metal sites. Hence, designing advanced (pre-)catalysts with a boosted pre-oxidation reaction is of great importance in improving the UOR performance and thus accelerating the coupled reactions. In this feature article, we discuss the significant role of the pre-oxidation process during the urea electro-oxidation reaction, and summarize detailed strategies and recent advances in promoting the pre-oxidation reaction, including the modulation of the crystallinity, active phase engineering, defect engineering, elemental incorporation and constructing hierarchical nanostructures. We anticipate that this feature article will offer helpful guidance for the design and optimization of advanced (pre-)catalysts for UOR and related energy conversion applications.