A nano-sized LiMnPO4@C core@shell structure was prepared through a facile two-step method. Oleylamine was introduced in the synthesis process using as both solvent and carbon source. The LiMnPO4@C structure has a particle size smaller than 40nm with uniform 2–3nm carbon coating layers, which interweave to form a secondary micrometer-sized mesoporous structure. The as-prepared LiMnPO4@C showed a high capacity of 168mAhg−1 at 0.1C and 105mAhg−1 at 5C applied as a cathode electrode for lithium ion batteries. The thin layer carbon coating not only increases LiMnPO4 in electronic and ionic conductivity, but also enhances its cycling ability by stabilizing the solid electrolyte interface.