Development of highly stabilized and reversible cathode materials has become a great challenge for sodium‐ion batteries. O′3‐type layered Mn‐based oxides have deserved much attention as one of largely reversible‐capacity cathodes featured by the resource‐rich and low‐toxic elements. However, the fragile slabs structure of typical layered oxides, low Mn‐ion migration barriers, and Jahn–Teller distortion of Mn3+ have easily resulted in the severe degradation of cyclability and rate performances. Herein, a new queue‐ordered superstructure is built up in the O′3‐NaMn0.6Al0.4O2 cathode material. Through the light‐metal Al substitution in O′3‐NaMnO2, the MnO6 and AlO6 octahedrons display the queue‐ordered arrangements in the transition metal (TM) slabs. Interestingly, the presence of this superstructure can strengthen the layered structure, reduce the influence from Jahn–Teller effect, and suppress the TM‐ions migrations during long‐terms cycles. These characteristics results in O′3‐NaMn0.6Al0.4O2 cathode deliver a high capacity of 160 mAh g−1, an enhanced rate capability and the excellent cycling performance. This research strategy can provide the broaden insight for future electrode materials with high‐performance sodium‐ions storage. A novel queue‐order NaMn0.6Al0.4O2 (NMA) is first prepared as high‐performance cathode material for sodium‐ion battery. The NMA exhibits a firmed layered structure based on queue‐ordered Mn0.6Al0.4O2 slabs, which result in NMA cathode delivers a high practical capacity of 160 mAh g−1, a remarkable rate performance and an excellent cycling life of 81% retention after 100 cycles.