Novel hybrid Li2MnSiO4 nanoparticles with carbon have been in-site synthesized by spray pyrolysis of a precursor solution, exhibiting a stable cycling performance with a high discharge capacity about 200 mAh/g. The TEM observation showed the unique morphology of Li2MnSiO4 particles with only 10-20 nm in size surrounded by carbon phase, which can contribute to a short diffusion path of Li+ ions and the easy relaxation of structural distortion through the delithiation/lithiation. The XRD, XANES, and EXAFS studies of the charged/discharged structures revealed that the long-range order of Li2MnSiO4 structure was destroyed by charge/discharge cycles but the local structure around Mn2+ cation was kept unchanged. (C) 2013 The Electrochemical Society. All rights reserved.