The kinetic properties of Li insertion in NASICON-type Li3V2(PO4)3 cathodes were enhanced substantially by Al3+ and Cl− multivalent substitutions of various concentrations. Pristine and carbon coated, Al-doped Li3V2(PO4)3 were also prepared by a conventional solid-state approach under optimized conditions. Samples phase purity was investigated through X-ray diffractometry. Li insertion was studied in half-cells at 3-4.8V vs. Li for the removal of 3mol of Li. Carbon-coated Li3V1.98Al0.02(PO4)2.99Cl0.01 showed the highest reversible insertion of 2.71mol of Li (178mAhg−1) at a current density of 0.2mAcm−2. It showed a capacity retention of over 80% after 100 cycles. Cl− substitution led to improved performance under harsh conditions of 15C rate and high temperature (50°C). The enhancement of Li ion kinetics was demonstrated through cyclic voltammetry in a two-electrode configuration and electrochemical impedance spectroscopy confirmed the enhanced conductivity.