The Fe2O3-coated LiNi1/3Co1/3Mn1/3O2 (NCM111-Fe) was successfully prepared via a co-precipitation reaction assisted by thermal decomposition of iron citrate. The crystal structure, morphologies and element condition of the samples were researched by XRD, SEM, TEM and XPS. The NCM111 was covered with Fe2O3-layer after thermal decomposition of iron citrate, and the existence of Fe2O3 layer did not change the pristine crystal structure of NCM111. Between 3.0 and 4.8V, the NCM111-Fe delivered an initial capacity of 192.5mAhg(-1) at 0.1C and 86.7% of the capacity remained after 100 cycles. In contrast, NCM111 exhibited an initial capacity of 187mAhg(-1) and only remained 63.5% after 100 cycles. The results indicated that the NCM111-Fe displayed weaker polarization, smaller charge-transfer resistance and better electrochemistry performance than the pristine sample.