The development of high‐performance cathode materials for next‐generation lithium‐ion batteries (LIBs) is urgently needed. Among the potential cathode candidates, ternary layer oxide LiNi1/3Co1/3Mn1/3O2 (LNCM) has attracted considerable attention due to its high voltage discharge, large theoretical specific capacity, stable chemical structure and low cost. However, Li+/Ni2+ cation mixing and low conductivity have resulted in poor long‐term cyclability, voltage drop and capacity degradation during high‐rate charging. To address these issues, a sol‐gel technique together with an annealing treatment was used to prepare LNCM with well‐defined structure and good morphology. The material obtained by heating the LNCM precursor at 850 °C for 12 h (LNCM‐850/12) exhibited an initial discharge specific capacity of 217.9 mAh g−1 at 0.2 C and maintained a high reversible capacity of 116.1 mAh g−1 after 200 cycles. The LNCM‐850/12 electrode also demonstrated superior rate capacity and exceptional cycling stability due to its well‐defined structure, low Li+/Ni2+ cation mixing and good morphology. These characteristics improve the electrical/ionic conductivity, reduce the charge transfer resistance and shorten the Li+ diffusion distance, ultimately accelerating the Li+ insertion and extraction. Overall, the careful control of calcination time in LNCM synthesis provides valuable insights for the development of advanced cathodes for LIBs.