Ni‐rich layered oxides have been intensively considered as promising cathode materials for next‐generation Li‐ion batteries. Nevertheless, the performance degradation caused by intergranular cracks and electrode/electrolyte interface parasitic reactions restricts their further application. Compared with secondary particles, single‐crystal (SC) materials have better mechanical integrity and cycling stability. However, the preparation of ultrahigh‐nickel layered SC cathode still remains a serious challenge. Herein, a novel LiOH‐LiNO3‐H3BO3 molten‐salt method is proposed to synthesize SC LiNi0.92Co0.06Mn0.02O2 with considerable crystallinity and uniformity. The critical impacts of calcination temperature and boric acid on the microstructure and electrochemical property of Ni‐rich layered oxides are systematically investigated. The results show that the crystal growth is promoted and the stability of crystal structure is improved by this synthesis method. In particular, the optimal electrode demonstrates a superior initial discharge capacity of 214.8 mAh g–1 with a high capacity retention of 86.3% over 300 cycles as tested by pouch‐type full cells at 45 ºC. This work not only prepares an ultrahigh‐nickel layered CS cathode with superior electrochemical performances, but also provides a feasible method for the synthesis of other CS layered cathode materials.