A new type of LiFePO4/C composite surrounded by a web containing both amorphous and crystalline carbon phases was synthesized by incorporating malonic acid as a carbon source using a high temperature solid-state method. SEM, TEM/SAED/EDS and HRTEM were used to analyze surface morphology and confirmed for the first time that crystalline carbon was present in LiFePO4/C composites. The composite was effective in enhancing the electrochemical properties such as capacity and rate capability, because its active component consists of nanometer-sized particles containing pores with a wide range of sizes. An EDS elemental map showed that carbon was uniformly distributed on the surface of the composite crystalline particles. TEM/EDS results clearly show a dark region that is LiFePO4 with a trace of carbon and a gray region that is carbon only. To evaluate the materials’ electrochemical properties, galvanostatic cycling and conductivity measurements were performed. The best cell performance was delivered by the material coated with 60wt.% malonic acid, which delivered first cycle discharge capacity of 149mAhg−1 at a C/5 rate and sustained 222 cycles at 80% of capacity retention. When carboxylic acid was used as a carbon source to produce LiFePO4, overall conductivity increased from 10−5 to 10−4 Scm−1, since particle growth was prevented during the final sintering process.