A combination of Al-27 magic-angle spinning (MAS)/multiple quantum (MQ)-MAS, C-13-H-1 CPMAS, and C-13-{Al-27} transfer of population in double-resonance (TRAPDOR) nuclear magnetic resonance (NMR) were used for the structural elucidation of the aluminum alkoxides aluminum ethoxide, aluminum isopropoxide, and aluminum tertiarybutoxide. Aluminum alkoxides exist as oligomers with aluminum in different coordinations. High-resolution 27Al MAS NMR experiments with high-spinning speed distinguished the aluminum atoms in different environments. The Al-27 MAS NMR spectrum gave well-resolved powder patterns with different coordinations. Z-filter MQ-MAS was performed to obtain the number and types of aluminum environments in the oligomeric structure. C-13-H-1 CPMAS chemical shifts resolved the different carbon species (-CH3, -CH2, -CH-, and =C=) in the structures. C-13-{Al-27} TRAPDOR experiments were employed to obtain relative Al-C dipolar interactions and to distinguish between terminal and bridging alkoxides in the crystallographic structures. The complete characterization of selected aluminum alkoxides using advanced NMR methods has evidenced the tetrametic structure for aluminum isopropoxide and the dirneric structure for aluminum tertiary-butoxide, as reported in the literature, and proposed a polymeric structure for aluminum ethoxide.