In this work, the spinel LiMn2O4 cathode material was prepared by high-temperature solid-phase method and further optimized by co-modification strategy based on the Mg-doping and octahedral morphology. The octahedral LiMn1.95Mg0.05O4 sample belongs to the spinel cubic structure with the space group of Fd3m, and no other impurities are presented in the XRD patterns. The octahedral LiMn1.95Mg0.05O4 particles show narrow size distribution with regular morphology. When used as cathode material, the obtained LiMn1.95Mg0.05O4 octahedra shows excellent electrochemical properties. This material can exhibit high capacity retention of 96.8% with 100th discharge capacity of 111.6 mAh g-1 at 1.0 C. Moreover, the rate performance and high-temperature cycling stability of LiMn2O4 are effectively improved by the co-modification strategy based on Mg-doping and octahedral morphology. These results are mostly given to the fact that the addition of magnesium ions can suppress the Jahn-Teller effect and the octahedral morphology contributes to the Mn dissolution, which can improve the structural stability of LiMn2O4. © 2019 by the authors.