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 3-4.8 V vs. Li for the removal of 3 mol of Li. Carbon-coated Li(3)V(1.98)A(10.02)(PO4)(2.99)Cl-0.01 showed the highest reversible insertion of 2.71 mol of Li (178 mAh g(-1)) at a current density of 0.2 mA cm(-2). It showed a capacity retention of over 80% after 100 cycles. Cl- substitution led to improved performance under harsh conditions of 15 degrees C rate and high temperature (50 degrees 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. (C) 2013 Elsevier Ltd. All rights reserved.