Monoclinic Li3V2−x Al x (PO4)3 with different Al3+ doping contents (x =0, 0.05, 0.08, 0.10 and 0.12) have been prepared by a facile aluminothermal reaction. Aluminum nanoparticles have been used as source for Al3+ and nucleus for Li3V2−x Al x (PO4)3 nucleation as well as reducing agent in the aluminothermal strategy. The products were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and electrochemical methods. The XRD results show that the as-obtained Li3V2−x Al x (PO4)3 has a phase-pure monoclinic structure, irrespective of the Al3+ doping concentration. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) results reveal that the charge-transfer resistance of the Li3V2(PO4)3 is reduced and the reversibility is enhanced after V3+ substituted by Al3+. In addition, The Li3V2−x Al x (PO4)3 phases exhibit better cycling stability than the pristine Li3V2(PO4)3.