Core-shell Li3V2(PO4)3@C nanostructured composites were prepared via a sol-gel route followed byhydrothermal treatment. XRD patterns showed that Li3V2(PO4)3 has a monoclinic structure with space groupP21/n. TEM images exhibited that Li3V2(PO4)3 particles are encapsulated with a carbon shell ~10 nm inthickness. Compared with pure Li3V2(PO4)3, core-shell Li3V2(PO4)3@C composites presented enhancedelectrochemical Li ion intercalation performances. Cyclic voltammetry and electrochemical impedancespectroscopy disclosed that carbon shells improved Li ion diffusion and electrical conductance significantlyand also retarded formation of solid electrolyte interphase film of Li3V2(PO4)3 cathode materials.