A novel method for the preparation of hierarchically porous LiFePO4 electrode materials for lithium ion batteries has been investigated. A meso/macroporous carbon monolith, a conductive framework, was prepared and infiltrated with the LiFePO4 precursors to increase the electrode/electrolyte interface and improve the rate capability of the battery. The final LiFePO4/carbon monoliths feature a meso/macroporous hierarchical structure. The monoliths were calcined at increasing temperatures, from 650 to 800 °C, to determine the structural and sintering effects on the electrochemical properties of the materials. The samples were characterized using SEM, TEM, nitrogen sorption, and XRD analysis prior to electrochemical testing. The results showed that the capacity of the LiFePO4/carbon electrodes achieved 82% of the theoretical capacity at 0.1C discharge rate.