Al2O3-modified Li(Ni1/3Co1/3Mn1/3)O2 is synthesized by a modified Al2O3 coating process. The Al2O3 coating is carried out on an intermediate, (Ni1/3Co1/3Mn1/3)(OH)2, rather than on Li(Ni1/3Co1/3Mn1/3)O2. As a comparison, Al2O3-coated Li(Ni1/3Co1/3Mn1/3)O2 also is prepared by traditional Al2O3 coating process. The effects of Al2O3 coating and Al2O3 modification on structure and electrochemical performance are investigated and compared. Electrochemical tests indicate that cycle performance and rate capability of Li(Ni1/3Co1/3Mn1/3)O2 are enhanced by Al2O3 modification without capacity loss. Al2O3 coating can also enhance the cycle performance but cause evident capacity loss and decline of rate capability. The effect of Al2O3 coating and Al2O3 modification on kinetics of lithium-ion transfer reaction at the interface of electrode/electrolyte is investigated via electrochemical impedance spectra (EIS). The result support that the Al2O3 modification increase Li+ diffused coefficient and decrease the activation energy of Li+ transfer reaction but the traditional Al2O3 coating lead to depression of Li+ diffused coefficient and increase of activation energy.