As a cathode material for commercial lithium rechargeable battery, Al-doped and Al2O3-coated LiCoO2 were structurally characterized and compared by using solid-state 7Li and 27Al magic angle spinning (MAS) NMR. The structural states of lithium and aluminum in those samples were successfully identified by calculation of NMR spectra. 7Li MAS NMR spectra of samples had shown similar features having more than three lithium sites, which were determined as quadrupole coupling constant with the same asymmetric parameter (η = 0.1); C Q = 1.10MHz for octahedral site, and C Q = 2.97MHz and C Q = 3.83MHz for shoulders. 27Al MAS NMR spectra of samples, however, showed significant difference in two observed aluminum sites. In the simulation of NMR spectrum for Al2O3-coated LiCoO2, the values of C Q and η were obtained; 4.45MHz and η = 0.86 for tetrahedral site and 4.31MHz and η = 0.81 for octahedral.