ABSTRACT A series of spherical hierarchical LiNi1−x−yCoxAlyO2 (0<x, y<0.2) were successfully synthesized via a novel and simple cation exchange process. Specifically, spherical flowerlike Ni1−x−yCoxAly(OH)2+y (0<x, y<0.2) were obtained from (Ni0.85Co0.15)3(NO3)2(OH)4 via the cation exchange between Al ion and Ni/Co ions while maintaining its morphology. Then, after calcination, the hierarchical spherical LiNi1−x−yCoxAlyO2 (0<x, y<0.2) could be easily obtained. Among these materials, the hierarchical spherical LiNi0.84Co0.14Al0.02O2 performs the discharge capacity of 190mAhg−1 at 20mAg−1 at the second cycle, while the material LiNi0.85Co0.15O2 obtained using the (Ni0.85Co0.15)3(NO3)2(OH)4 without ion exchange performs a discharge capacity of 165mAhg−1. Furthermore, the hierarchical spherical LiNi0.84Co0.14Al0.02O2 maintains the high capacity retention of 84.0% after 225 cycles at 200mAg−1. This work exploits a new and facile way to synthesize high capacity Al-contained layered metal oxides cathode materials.