LiFePO4 samples with preferred facets on the ac plane were prepared by the solvothermal method with or without well-dispersed amphiphilic carbonaceous material (ACM). The effects of ACM on the particle morphology, crystal orientation and electrochemical reactivity of the prepared LiFePO4 nanoparticles were investigated in detail. ACM serves a dual purpose. One purpose is facilitating the plate-like morphologies of LiFePO4 nanoparticles parallel to the b Pnma axis by decreasing the surface energy of (010) facets of newly created LiFePO4 nuclei. The other purpose is suppressing crystal growth along the [010] direction by adhering onto the (010) surface of LiFePO4 nanoplates. Furthermore, ACM coating was performed and optimized using a carbon coating precursor. The electrochemical properties of the prepared LiFePO4 particles were characterized by cyclic voltammetry (CV) and galvanostatic charge–discharge cycling tests. After the optimized coating of ACM, the ACM-intervened LiFePO4 composite was observed to deliver discharge capacities of 151.3 mAh g−1 at 1C and 132.2 mAh g−1 at 10C. Even after 1000 cycles at a high rate of 10C, the LiFePO4 cathode could maintain 80% of its initial capacity.