In this work, a LiFe0.5Mn0.5PO4/C (LFMP/C) material was prepared by a simple solid-state ball-mill method by using LiH2PO4, γ-MnO2, and hollow α-Fe2O3 nano-sized materials. Both γ-MnO2 and hollow α-Fe2O3 were synthesized by a hydrothermal process. LFMP/C composites coated with different amounts (1–3wt%) of Li4Ti5O12 (LTO) were synthesized by a sol-gel method. Their typical properties are studied using X-ray diffraction, micro-Raman spectroscopy, scanning electron microscopy/energy-dispersive X-ray spectroscopy, transmission electron microscopy, the AC impedance method, and the galvanostatic charge–discharge method. The results revealed that a 1 wt%-LTO-coated LFMP/C composite shows the highest performance among all LFMP/C composite samples. The long-term cycling performance of the LFMP/C composite improves considerably when the LTO ionic conductor is applied on it. Moreover, the 1 wt%-LTO-coated LFMP/C composite, which has the lowest fading rate, maintains high cycling stability at 1 C (141 mAh g−1) and 10 C (133 mAh g−1) at 55 °C after 100 cycles; by contrast, a bare LFMP/C sample, which demonstrates the highest fading rate, exhibits an unfavorable life cycle, and its discharge capacity decreases rapidly. The ionic conductor coating thus improves the high-temperature performance of LFMP/C composites. A LFMP/C-KS6/SiO2 full cell is assembled and tested.