A three-dimensionally ordered macroporous (3DOM) Li3V2(PO4)3/C cathode material with small-sized macropores (50-140 nm) is successfully synthesized using a colloidal crystal array. The 3DOM architecture is built up from fully densely sintered Li3V2(PO4)3/C nanocomposite ceramics particles. Such a 3DOM Li3V2(PO4)3/C micrometer sized particle combines the advantages of both Li3V2(PO4)3 nanocrystal and micrometer sized particle. The resultant 3DOM Li3V2(PO4)3/C nanocomposite exhibits a stable and highly reversible discharge capacity up to 151 mA g(-1) at 0.1 C, and an excellent high-rate capability of 132 mA g(-1) at 5 C in the voltage range of 3.0-4.4 V. Compared to the corresponding bulk nanocomposite, the 3DOM Li3V2(PO4)3/C cathode exhibits a significantly improved high-rate performance, which promises new opportunities in the development of high energy and high power lithium-ion batteries.