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Self-association of medium-chain alcohols in n-decane solutions has been studied by infrared absorption of the fundamental OH stretching vibration. The alcohols investigated were 1-propanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-butanol, 1-pentanol, and 1-hexanol. Infrared spectra were acquired for varying alcohol molalities, the highest concentration being 0.2 mol/kg. The spectra for each alcohol were collected in a data matrix. The bilinear multicomponent data were successfully resolved into spectra and concentration profiles by a multivariate method. The result indicates that monomers dominate the spectral variance in the low-molality region, while cyclic oligomers dominate in the upper concentration range. It further indicates that minor amounts of open-chain aggregates may be present. The monomer and cyclic tetramer appear to be the dominant species, while the amount of open-chain aggregates was negligible even in the low-molality region. The equilibrium constants for the monomer–tetramer association reactions ( K1–4) were calculated by a least-squares method. The calculated values for the equilibrium constants, based on the molality, range from 138 to 106 for the linear alcohol molecules. The result shows that 1-butanol, 1-pentanol, and 1-hexanol have similar constants, while 1-propanol displays a markedly higher value. The equilibrium constants obtained for 2-methyl-1-propanol and 2-methyl-2-propanol were 77 and 39, respectively. The considerably lower values for the branched alcohol molecules indicate that steric interaction between the chain prevents self-association into larger aggregates.