•C/LiFePO4/MWCNTs nanoparticles were prepared combined with a hydrothermal approach and an electro-polymerization technology•The obtained electrode material presents high-rate ability and cyclic stability•The cathode material can be highly desirable for high power lithium ion batteriesNanosized C/LiFePO4/MWCNTs secondary particles were synthesized by a combination of hydrothermal progress and a facile electro-polymerization polyaniline process with simultaneous calcinations. In combination with the continuous three-dimensional (3D) networks 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 with a tap density of 1.78 g cm− 3, stable charge/discharge cycle ability. The synthesized LiFePO4 composite demonstrated an increased reversible capacity and better cycling ability compared to the bare LiFePO4, offering a discharge capacity of 169.9 mAh g− 1 (nearly to its the theoretical capability 170 mAh g− 1) at the C/10 rate and delivering a good rate performance with a capacity of 143.4 mAh g− 1 at a high rate of 20 C, and stable charge/discharge cycle ability (> 95% capacity retention after 200 charge/discharge cycles).This non-organic facile synthesize avenue can be highly desirable to prepare next-generation high-power lithium ion batteries.