The electrochemical performance of the carbon-coated Li3V2(PO4)3 (LVP/C) composite prepared through a carbon thermal reduction route has been investigated. The results show that the LVP/C composite exhibits reversible Li+ de-intercalating/intercalating behaviors with the swing potential in the range of −0.2 to 0.8V vs. SCE in a neutral Li2SO4 aqueous solution. It has also been found that the activated carbon (AC)//LVP/C asymmetric hybrid capacitor exhibits good electrochemical properties. The asymmetric hybrid capacitor shows sloping profiles in the galvanostatic charge–discharge curves with the operating voltage in the range of 0–1.7V and can work steadily. Both of the capacity retention and coulombic efficiency of the asymmetric hybrid capacitor can retain more than 90% after 1000 charge–discharge cycles at a current density of 250mAg−1. At the power density of 102Wkg−1, the energy density of the asymmetric hybrid capacitor is 35Whkg−1, and even at 2000Wkg−1, the energy density can achieve 5Whkg−1. In addition, we have found that the conductive additive such as acetylene black is not required during the electrode fabricating process with the LVP/C composite as an electrode material, and this will serve the interest of saving cost. This work could provide an evidence for the development of aqueous asymmetric hybrid capacitors using LVP/C as electrode materials.