Abstract Excess volume data on mixing for binary mixtures of γ-Butyrolactone with propan-1-ol, butan-1-ol, pentan-1-ol, hexan-1-ol, propan-2-ol, 2 methyl propan-1-ol, 3 methyl butan-1-ol, have been determined at 303.15 K. The VE values are negative over the whole range of composition in mixtures containing propan-1-ol, propan-2-ol, butan-1-ol, 2 methyl propan-1-ol, and 3 methyl butan-1-ol. In pentan-1-ol, however, VE is negative at lower molefractions and positive at higher molefractions, whereas in hexan-1-ol the value of VE are positive throughout the entire concentration range, which indicates significant interaction between γ-butyrolactone and the aliphatic and isomeric groups. These values are attributed to weak complex formation and predominating de-association of associated liquids by γ-butyrolactone. The results are ascribed to interactions between unlike molecules.