Abstract: The effects of carbonaceous materials on the physical and electrochemical performance of LiFePO₄/C hybrids are reviewed. The major role, advantages and disadvantages of carbon-based materials in LiFePO₄/carbon hybrids are discussed. The introduction of an in situ grown carbon coating would be beneficial to limiting the LiFePO₄ particle growth and increasing the electric conductivity. The structure and precursors of the in situ grown carbons have a great influence in the rate performance of the hybrids, which can be related to an improved electron and ion transfer rate. Deposition of LiFePO₄ into a carbonaceous matrix such as a templated membrane can increase the contact area between the active materials and the electrolyte, which favors a fast ion transport. The addition of conductive carbon and graphene would only effectively increase the electrical conductivity. In order to achieve an excellent electrochemical performance of LiFePO₄, it is necessary to take advantage of and to combine these approaches to optimize electron and ion transfer rates. Also, it is most important to minimize the carbon content in LiFePO₄/carbon hybrids to increase volumetric energy density and tap density when practical applications in electric vehicles are targeted.