Lithium iron phosphate/(carbon and ferrous phosphide) (LiFePO4/(C + Fe2P)) composite nanofibers are successfully synthesized by electrospinning and subsequent heat-treatment. We develop a novel aqueous solution with excellent spinnability, which contains dihydrogen phosphate, ferric citrate, and polymer. Heat-treatment temperature makes great effect on the product morphology and the formation of Fe2P phase. The Fe2P phase appears when the temperature increases to 750 degrees C, while too high treatment temperature of 850 degrees C results in the destruction of fibrous morphology. The LiFePO4/ (C + Fe2P) composite nanofibers synthesized using the temperature of 750 and 800 degrees C show high capacity for lithium-ion battery, possibly attributed to the small fiber diameter and good conductivity enhanced by Fe2P and carbon species.