The novel multi-substituted LiNi0.475Al0.01Cr0.04Mn1.475O3.95F0.05 cathode material is synthesized via a sol–gel method. The results show that this material has a well-defined cubic spinel structure, Fd3m space group. The excellent rate capability can be obtained from this material to deliver a discharge capacity of 136.6, 129.0, 119.9, 104.5 and 86.4mAhg−1 at rates of 0.2, 5, 10, 15 and 20C, respectively. It still exhibits satisfactory cycle stability at room temperature (20°C) and elevated temperature (55°C), achieving 128.6 and 129.5mAhg−1 at 1C with the capacity retention of 98% and 99.7% after 100 cycles, respectively. Besides, the favorable rate cycle performance at 55°C has been shown to retain 95.2% of the maximum discharge capacity (102.7mAhg−1) at 10C after 100 cycles. The stable structure, high reversibility and electrochemical reaction kinetics afforded by multiple ions existing in the spinel appear to contribute to the excellent electrochemical performance.