A highly porous Ni@MIL-101catalyst for urea oxidation was synthesized by anchoring Ni into a Cr-based metal-organic framework, MIL-101, particles. The morphology, structure, and composition of as synthesized Ni@MIL- 101 catalysts were characterized by X-Ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. The electro-catalytic activity of the Ni@MIL-101catalysts towards urea oxidation was investigated using cyclic voltammetry. It was found that the structure of Ni@MIL-101 retained that of the parent MIL-101, featuring a high BET surface area of 916 m2 g-1, and thus excellent electro-catalytic activity for urea oxidation. A urea/H2O2 fuel cell with Ni@MIL-101 as anode material exhibited an excellent performance with maximum power density of 8.7 mWcm-2 with an open circuit voltage of 0.7 V. Thus, this work shows that the highly porous three-dimensional Ni@MIL-101 catalysts can be used for urea oxidation and as an efficient anode material for urea fuel cells.