Lithium vanadium oxide (Li3VO4, LVO) is a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity (394 mAh g−1) and safe working potential (0.5–1.0 V vs. Li+/Li). However, its electrical conductivity is low which leads to poor electrochemical performance. Graphene (GN) shows excellent electrical conductivity and high specific surface area, holding great promise in improving the electrochemical performance of electrode materials for LIBs. In this paper, LVO was prepared by different methods. SEM results showed the obtained LVO by sol-gel method possesses uniform nanoparticle morphology. Next, LVO/GN composite was synthesized by sol-gel method. The flexible GN could improve the distribution of LVO, forming a high conductive network. Thus, the LVO/GN composite showed outstanding cycling performance and rate performance. The LVO/GN composite can provide a high initial capacity of 350.2 mAh g−1 at 0.5 C. After 200 cycles, the capacity of LVO/GN composite remains 86.8%. When the current density increased from 0.2 C to 2 C, the capacity of LVO/GN composite only reduced from 360.4 mAh g−1 to 250.4 mAh g−1, demonstrating an excellent performance rate.