Concentration-gradient layered Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2 oxide with Ni-rich in the core and Mn-rich in the surface region has been synthesized through a condition-controlled tank reactor reaction. While the Ni-rich core facilitates high capacity, the Mn-rich surface enables good cyclability and thermal stability. The concentration-gradient sample exhibits a higher capacity of 204mAhg−1 at C/5 rate with superior cyclability and thermal stability compared to the constant-concentration LiNi0.62Co0.14Mn0.24O2 sample, which has the same net Ni, Co, and Mn contents as those present in the concentration-gradient sample. The concentration-gradient sample was also coated with a thin layer of Al2O3 on the surface to stabilize the electrode/electrolyte interface and thereby further improve the electrochemical performance. Both the structural (gradient structure) and surface (Al2O3 coating) modifications help suppress side reactions between electrode and electrolyte and reduce the decline in voltage during cycling. The Al2O3-coated concentration-gradient sample exhibits improved long-term cyclability, rate capability, and thermal stability compared to the pristine uncoated sample.