In this work, N-doped graphene and carbon co-modified Li3V2(PO4)3 composites (LVP/NGC) are successfully fabricated through a xerogel method for the first time. The obtained architecture combines two types of electronic contact with Li3V2(PO4)3 particles: the point-to-face contact of N-doped graphene and the face-to-face contact of N-doped carbon coating layers. Profiting from the favorable complex structure, graphene and carbon coating layers offer an extraordinary network for electron transfer and hence an excellent long-term and high-rate performance. Even tested at the rate of 40 C, the reversible capacity still maintains 86.9 mAh g−1 after 800 cycles without any fading. This work provides a promising route to improve the long-term and high-rate performance of cathodes for LIBs and enlightens us on exploring preferable strategies to develop advanced electrode materials for other energy storage devices.