Nano-sized composite with LiFePO4-core and carbon-shell was synthesized via a facile route followed by heat treatment at 650°C. X-ray diffraction (XRD) shows that the core is well crystallized LiFePO4. The electron microscopy (SEM and TEM) observations show that the core-shell structured LiFePO4/C composite coating with whole carbon shell layer of ∼2.8nm, possesses a specific surface area of 51m2 g−1. As cathode material for lithium ion battery, the core-shell LiFePO4/C composite exhibits high initial capacity of 161mAhg−1 at 0.1C, excellent high-rate discharge capacity of 135mAhg−1 at 5C and perfect cycling retention of 99.6% at 100th cycle. All these promising results should be contributed to the core-shell nanostructure which prevents collapse of the particle structure in the long-term charge and discharge cycles, as well as the large surface area of the nano-sized LiFePO4/C composite which enhances the electronic conductivity and shortens the distance of lithium ion diffusion.