Spherical Li[Ni0.8Co0.2−x Mn x ]O2 (x =0, 0.1) with phase-pure and well-ordered layered structure have been synthesized by heat-treatment of spherical [Ni0.8Co0.2−x Mn x ](OH)2 and LiOH·H2O precursors. The structure, morphology, electrochemical properties, and thermal stability of Li[Ni0.8Co0.2−x Mn x ]O2 (x =0, 0.1) were studied. The average particle size of the powders was about 10–15μm and the size distribution was narrow due to the homogeneity of the metal hydroxide [Ni0.8Co0.2−x Mn x ](OH)2 (x =0, 0.1). The Li[Ni0.8Co0.2−x Mn x ]O2 (x =0, 0.1) delivered a discharge capacity of 197–202mAhg−1 and showed excellent cycling performance. Compared to Li[Ni0.8Co0.2]O2, Li[Ni0.8Co0.1Mn0.1]O2 exhibited greater thermal stability resulting from improved structural stability due to Mn substitution.