A templated freeze-drying method is developed to prepare the porous LiFePO4 materials with the controlled pore size and porosity, by conveniently adjusting the size and content of the template in the precursor solution. The morphology and structure of the porous LiFePO4 materials are characterized and the relavant electrochemical lithium-insertion performances are systematically studied. It’s found that the porous characteristics play a critical role in the lithium-ion intercalation processes and significantly affect the power capability of LiFePO4. The optimized porous LiFePO4 material presents remarkable specific capacity (167mAhg−1 at 0.1 C), rate capability (151mAhg−1 at 1 C and 110mAhg−1 at 10 C) and cycling stability (99.3% retention after 300 cycles at 1 C). These findings demonstrate that the electrochemical performance of the electrode material can be purposely tuned and remarkably improved by the rational design and introduction of the suitable pores, which open up new strategies for the synthesis of advanced porous materials for the lithium-ion power battery applications.