The LiTi2(PO4)3 has been successfully synthesized by a PEG (polyethylene glycol, mean molecular weight of 2000) based sol–gel route at a relative low temperature. For further improve its electrochemical properties, a ball milling process with acetylene black has been used to form LiTi2(PO4)3/C nanocomposite. The samples are characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Electrochemical performance of the samples is characterized by the charge–discharge test and cyclic voltammetry. The results show that the ball milling process enables LiTi2(PO4)3 nanoparticles networked with conductive acetylene black, which offered higher electrochemical performance. The LiTi2(PO4)3/C nanocomposite delivers a higher specific capacity, enhanced rate capability, and better cyclability.