Li3V2(PO4)3/C (LVP/C) is synthesized by an improved sol–gel method and modified with various amounts of Ti3SiC2 (TSC). It is found that both electronic and ionic conductivities are increased simultaneously with one single addition due to the nanolaminated structure of TSC. TSC not only constitutes continuous electron pathways via a “point-to-plane” conducting mode, which improves the electronic conductivity, but also enhances lithium ionic conductivity. Therefore, electrochemical performances of TSC-modified samples are significantly improved. TSC-modified samples exhibit improved cyclic stability, rate performance and initial discharge capacity at high rates. An extremely low charge transfer resistance (5.57 Ω) and significantly reduced polarization were obtained. The 4 wt% TSC-modified LVP/C sample exhibits the best electrochemical performances in the voltage range of 3.0–4.8 V, especially at high rates. It shows initial discharge capacity of 114.5 mAh g−1 at 10 C, while the discharge capacity of the pristine sample is only 37.2 mAh g−1 at the same rate. The 4 wt% TSC-modified LVP/C sample holds capacity retention of 88.5% at 10 C after 200 cycles, which is much higher than that of pristine one. A model of double-decker bus is proposed to understand the significant improvements of both electronic and ionic conductivities.