Carbon coated LiFePO4 (LiFePO4/C) with different contents of high electron conductive iron phosphide phase was synthesized by an aqueous sol–gel method in a reductive sintering atmosphere. Different synthesis parameters were used for adjusting the microstructure and phase compositions of the products. The effects of the carbon coating and iron phosphides on the electrochemical properties of the LiFePO4/C electrodes were studied by means of testing the discharge capacities at rates of 0.1–5C (1C =170mAhg−1) and analyzing the CV curves. The results show that carbon coating in a content of 1.5wt.% derived from the carbon source of ethylene glycol greatly decreases the particle size of LiFePO4 in one order in the specific surface area, and significantly improves the rate capability of LiFePO4. The effect of the content of FeP on the capacity of the carbon coated LiFePO4 was different at different discharge rates. Increasing the content of FeP from 1.2 to 3.7wt.% slightly decreases the capacity of LiFePO4/C at low discharge rate (0.1C and 1C), but obviously increases the capacity of LiFePO4/C when the discharge rate is increased to 5C. For the carbon free sample, even it also has 1.8wt.% FeP, it still possesses poor capacity due to the large particle size of LiFePO4 and the lack of conductivity. And too much iron phosphides lowers the discharge capacity of the electrode since they are inert for the deinsertion/insertion of lithium ion.