We developed a novel cathode electrode system composed of ultra highly porous structured LiFePO4/carbon composite for lithium ion batteries by a gelation-freezing (GF) method. This unique technique can be used to provide various shaped components by use of specific molds, and varying the freezing temperature could control the micrometer-sized cylindrical pore size and wall thickness in the porous composite. Film shapes of carbons that originate in the gelatin were found in the porous LiFePO4/carbon composite cathodes. The porous composite cathode shows a good electrochemical performance at a low current density, despite the low carbon content. Charge/discharge capacities for the LiFePO4/carbon composites decreased with decreasing gel-freezing temperature. The template-free GF method for fabricating the porous LiFePO4/carbon composite opens up a new route to develop electrodes with controlled morphologies for applications in high power lithium batteries. (C) 2012 Elsevier B.V. All rights reserved.