Microscopic environments and dynamics in LiCoO2 systems were probed by L7i nuclear magnetic relaxation measurements with regard to the structural defects as revealed by x-ray diffraction and electron spin resonance measurements. Thus, the structural defects of differing degrees, associated with Li vacancies, were well accounted for in the temperature-dependent spin-lattice relaxation rate analysis, and in the structural and dynamical inhomogeneity as derived from the relaxation patterns.