Carbon-coated lithium iron phosphate (C/LFP) composite has been synthesized at 650°C in an N2 atmosphere by calcination/pyrolysis method using amorphous FePO4·xH2O nanopowders as the precursor. The key factor for preparing the C/LFP composites is to start with the co-precipitation synthesis of FePO4·xH2O spheres at pH 3. The C/LFP composite exhibits good crystallinity, well-dispersed particles of 250nm, and in situ carbon coating (thickness: 3–4nm) over the surface of LFP crystallites. The as-prepared C/LFP composite delivers a high discharge capacity of 162.1 and 119.7mAhg−1 at rates of 0.1 and 5C, respectively. This enhanced rate capability is ascribed to the synergetic effect on the C/LFP cathode that combines (i) quasi-spherical nanoparticles and (ii) a thin carbon layer. Additionally, the C/LFP composite presents a high tap density (1.34gcm−3), inducing high performance without sacrificing the volume energy density. Accordingly, the result reveals an efficient approach for synthesizing the C/LFP materials with excellent performance, which is beneficial for large-scale applications such as hybrid electric vehicles.