Composites of monoclinic Li3−x M′ x V2−y M″2y (PO4)3 (M′=K, M″=Sc, Mg+Ti) with carbon were synthesized by solid-state reaction using oxalic acid or 6% H2/Ar gas mixture as reducing agents at sintering temperature of 850°C. The samples were characterized by X-ray diffraction (XRD), voltammetry and electrochemical galvanostatic cycling. The capacity of Li3V2(PO4)3 synthesized using hydrogen as the reducing agent was 127mAhg−1 and decreased to 120mAhg−1 after 20 charge–discharge cycles. The substitution of lithium and vanadium for other ions did not result in the improvement of the electrochemical characteristics of the samples.