In order to combine the advantages of core-shell and concentration-gradient Li[Ni1-xMx]O2 materials, a novel structured Li[Ni0.66Co0.1Mn0.24]O2 (NSLi[Ni0.66Co0.1Mn0.24]O2) cathode material is facilely synthesized from core-shell precursor [(Ni0.8Co0.1Mn0.1)0.6(Ni0.45Co0.1Mn0.45)0.4](OH)2 via ion diffusion during high temperature calcination. NSLi[Ni0.66Co0.1Mn0.24]O2 is constructed by core layer, concentration-gradient layer and shell layer. From the detailed comparative investigations, it is found that NSLi[Ni0.66Co0.1Mn0.24]O2 delivers remarkably improved cycle life and thermal stability compared with normal Li[Ni0.66Co0.1Mn0.24]O2 (NLi[Ni0.66Co0.1Mn0.24]O2).