LiFePO₄/N-doped C composites with core–shell structures were synthesized by a convenient solvothermal method. Cetyltrimethylammonium bromide (CTAB) and glucose were used as nitrogen and carbon sources, respectively. The growth of LiFePO₄ nanocrystals was regulated by CTAB, resulting in an average particle size of 143 nm for the LiFePO₄/N-doped C. The N atoms existed in the carbon of LiFePO₄/N-doped C in the form of pyridinic N and graphitic N. The LiFePO₄/N-doped C composites delivered discharge specific capacities of 160.7 mAh·g⁻¹ (0.1 C), 128.4 mAh·g⁻¹ (5 C), and 115.8 mAh·g⁻¹ (10 C). Meanwhile, no capacity attenuation was found after 100 electrochemical cycles at 1 C. N-doping enhanced the capacity performance of the LiFePO₄/C cathode, while the core–shell structure enhanced the cycle performance of the cathode. The electrochemical test data showed a synergistic effect between N-doping and core–shell structure on the enhancement of the electrochemical performance of the LiFePO₄/C cathode.