Li3V2(PO4)3 nanocrystals (5–8 nm) embedded in a nanoporous carbon matrix attached onto reduced graphene oxide nanosheets (LVP-NC@NPCM@rGO) are synthesized by a facile approach. The rGO sheets not only form the interconnected conducting scaffold to enhance the charge transfer but also act as the heterogeneous nucleation site to facilitate the growth of nanograins of LVP. The nanoporous carbon acts as the nanocontainer to enhance the electrolyte/active material interaction and also inhibit the grain growth of Li3V2(PO4)3. This leads to the fast kinetics of the Li ion transfer and the excellent cathode performance, especially at high current densities. Binder-free cathodes can be prepared based such LVP-NC@NPCM@rGO sample, which shows high specific capacities, stable cyclabilities and excellent rate capabilities in the voltage ranges of 3.0–4.3 and 3.0–4.8 V.