Three dimensional (3D) porous C/LiFePO4/MWCNTs was synthesized by a hybrid of in situ sol gel strategy and a facile electro-polymerization polyaniline technique and a simultaneous sintering progress. In combined with the 3D hierarchical pore topologies and high electronic conduction facilitating the kinetics of both electron transport and lithium ion diffusion within the particles, the optimized electrodes exhibit an ultrahigh rate capacity, stable charge/discharge cycle ability, and a comparative volume capacity. The synthesized LiFePO4 composite offers a discharge capacity of 169.6mAhg−1 (nearly to its the theoretical capability 170mAhg−1) at the C/10 rate and delivers a good rate performance with a capacity of 141.9mAh g−1 at a high rate of 20C, and stable charge/discharge cycle ability (>95% capacity retention after 200 charge/discharge cycles).This non-organic facile synthesize avenue can be high desirable to prepare high-power electrode materials