LiFePO4/C matrixes are synthesized by a facile sol–gel method using pollen as both the bio-template and carbon source. Nano-LiFePO4 is brought into the porous carbon structures as the carbonized pollen templates. With this novel microstructure, the obtained LiFePO4/C matrixes show quite excellent electrochemical performance and rather good rate performance without any conductive agents added. This is ascribed to the short particle size of the well crystalline nano-LiFePO4 and good electronic interconnect supplied by the carbonized bio-templates.