A new approach to synthesize LiFePO4/C composite without the need of ball milling was developed by using complex carbon source. The esterification reaction between citric acid and sucrose during the drying process fosters the well-mixing of precursor materials, which contributes to the small particle size, porous network, large surface area and good electrochemical performances of LiFePO4/C composite. The ratio of sucrose to citric acid affects the morphology and electrochemical performance of LiFePO4/C. This study offers a new method to optimize the morphology of LiFePO4/C composite by controlling the interaction between different precursors during precursor treatment, such as the esterification reaction between carboxylic acid and sugar. The method developed is simple, requires inexpensive starting materials and the final product gives good electrochemical performance; therefore, it may be of great interest in the mass production of LiFePO4/C cathode material. (C) 2012 Elsevier B.V. All rights reserved.