This paper reports sol–gel derived nanostructured LiFePO4/carbon nanocomposite film cathodes exhibiting enhanced electrochemical properties and cyclic stabilities. LiFePO4/carbon films were obtained by spreading sol on Pt coated Si wafer followed by ambient drying overnight and annealing/pyrolysis at elevated temperature in nitrogen. Uniform and crack-free LiFePO4/carbon nanocomposite films were readily obtained and showed olivine phase as determined by means of X-Ray Diffractometry. The electrochemical characterization revealed that, at a current density of 200mA/g (1.2C), the nanocomposite film cathodes demonstrated an initial lithium-ion intercalation capacity of 312mAh/g, and 218mAh/g after 20 cycles, exceeding the theoretical storage capacity of conventional LiFePO4 electrode. Such enhanced Li-ion intercalation performance could be attributed to the nanocomposite structure with fine crystallite size below 20nm as well as the poor crystallinity which provides a partially open structure allowing easy mass transport and volume change associated with Li-ion intercalation. Moreover the surface defect introduced by carbon nanocoating could also effectively facilitate the charge transfer and phase transitions.