We report the structural and electronic characterization of Li2FeSiO4 synthesized by solid-state reaction. X-ray diffraction, Raman scattering, Fourier transform infrared (FTIR) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and magnetization measurements are analyzed. Magnetic susceptibility experiments give evidence that Li2FeSiO4 powders possess an antiferromagnetic ordering below T N =25K due to long range Fe–O–Li–O–Fe interactions. Analysis of the paramagnetic region giving the Curie–Weiss parameters θ p =−93.5K and C p =4.13emuKmol−1 shows the divalent state of Fe cations. Electron paramagnetic resonance experiments confirm this electronic configuration. Electrochemical measurements were carried out in lithium cells with LiTFSI in a poly(ethylene oxide) (PEO) polymer electrolyte at 80°C. The resulting cyclic voltammogram indicates a stable structure for the first cycle with redox peaks at 2.80 and 2.74V versus Li0/Li+.