This work introduces a new method to synthesize Li3Fe2(PO4)3 nanoparticles in the nanopowder form and study its electrochemical performance by cyclic voltammetry and battery tests. Li3Fe2(PO4)3 is synthesized by the gel combustion method based on polyvinyl alcohol (PVA) as gel making agent. The optimum conditions of the synthesis include 8wt% PVA, 0.34wt% lithium slat, 1wt% iron salt, 0.57wt% ammonium dihydrogen phosphate, ethanol–water 50:50 as solvent, 675°C combustion temperature and 4h combustion time. Characterization of the samples is performed by the scanning electron microscopy (SEM), transmission electron microscopy (TEM), EDX analysis, XRD patterns, BET specific surface area and DSL size distribution. In the optimum conditions, a nanopowder is obtained that consisting of uniform nanoparticles with an average diameter of 70nm. The optimized sample shows 12.5m2 g−1 specific surface areas. Cyclic voltammetry (CV) studies show that the synthesized compound has good reversibility and high cyclic stability. The CV results are confirmed by the battery tests. The obtained results show that the synthesized cathodic material has high practical discharge capacity (average 125.5mAhg−1 approximately same with its theoretical capacity 128.2mAh−1) and long cycle life.