Microporous and crystalline nickel phosphate nanorods with VSB-5 (Versailles-Santa Barbara-5) structure were uniformly grown around the skeleton of nickel foam under hydrothermal condition in the presence of lithium dihydrogen phosphate. The VSB-5 nanorods exhibited open-framework structure, nanoporosity with a pore diameter of about 1 nm, and typical molecular sieves with zeolitic properties, making them a promising catalyst material for urea oxidation reaction (UOR). A catalyst layer of reticulated VSB-5 nanorods grown on the nickel foam could provide abundant micro-, meso-, and macro-scale pores for hosting electrolyte and expediting the movement of electron, electrolyte, and gaseous products. Electrochemically active surface area (EASA) of the VSB-5 electrode with unique pore structure was considerably greater than that of the nickel hydroxide electrode with granular particles and dense interior. Large EASA and high valence state of nickel species accounted for the superior electrocatalytic performance of the VSB-5 electrode towards UOR compared with the nickel hydroxide electrode. The VSB-5 electrode exhibited higher current density (160 mA cm−2) at 0.6 V vs. SCE (saturated calomel electrode) and lower onset potential (0.27 V vs. SCE) than the nickel hydroxide electrode (75 mA cm−2 and 0.28 V) obtained from the cyclic voltammograms.