Li3VO4 nanoparticles in N-doped carbon with porous structure are synthesized using supermolecular aggregates formed by melamine and citric acid as the nitrogen source, via a dry-freezing process, followed with a calcination. Nitrogen doping enhances the interaction between Li(3)VO(4 )and carbon, reduces the charge-transfer resistance over the interface, and restrains the pulverization and aggregation upon cycling. The design of porous structure accelerates the permeation of electrolyte and increases the contact between active materials and electrolyte. The synergistic effects between N-doped carbon and porous structure significantly improve the electrochemical performances. Thus, this composite delivers a capacity of 405.1 mAh g(-1) at 0.1 A g(-1) or 199.9 mAh g(-1) at 10.0 A g(-1) within 0.2-3.0 V. After 1000 cycles at 4.0 A g(-1), the specific capacity is still kept as 236.6 mAh g(-1) . By pairing with commercial LiCoO2, this composite delivers a high energy density of 195.05 Wh kg(total)(-1) at 70.52 W kg(total)(-1), and 94.06 Wh kg(total)(-1) at 3.9 kW kg(total)(-1).