Spherical porous LiFePO4/C (LFP/C) composite materials were prepared by employing a solid-state (SS) method and a spray dry (SP) method. The surface modification was conducted on the spherical LFP/C composite using 1–5wt.%Li4Ti5O12 (LTO) to improve the rate capability and the cycle stability properties at low temperature (0°C) and elevated temperature (55°C). The characteristic properties were examined through X-ray diffraction, micro-Raman spectroscopy, scanning electron microscopy, an AC impedance method, and galvanostatic charge–discharge method. The characteristic properties of the SS-LFP/C, SP-LFP/C, and LTO-coated SP-LPF/C composites were studied and compared. The 3wt.%LTO-coated SP-LFP/C composite exhibited the most favorable performance among the samples. It exhibited discharge capacities of 150, 141, 131, 110, 103, and 84mAhg− 1, at rates of 0.2C, 0.5C, 1C, 3C, 5C, and 10C, respectively. It was also found that the 3wt.%LTO-coated SP-LFP/C composite shows the best cycling stability performance at elevated temperature of 55°C. The LTO-coated SP-LFP/C composite was demonstrated to be suitable for high-temperature and high-power application in lithium-ion batteries.