Solvatochromic studies on quinoline (Q) were performed in binary methanol/ N, N-dimethylformamide (MeOH/DMF), propan-1-ol/ N, N-dimethylformamide (PrOH/DMF), and pentan-1-ol/ N, N-dimethylformamide (PeOH/DMF), solvent mixtures, at 25.0 °C, using UV–Vis spectrometry. The Preferential Solvation Model of Bosch and Rosés was applied to the molar transition energy values corresponding to the absorption maximum of quinoline, E T(Q), over the whole range of mole fraction of N, N-dimethylformamide, x(DMF), and the influence of solvent polarity on these energy values was evaluated. The results show that the solvatochromic response model of Q dissolved in binary HBD/DMF mixtures was different from the HBD/cyclohexane solvent mixtures studied before. The studies reveal a synergistic solvation behaviour for higher mole fractions of DMF and a preferential solvation of Q by the less polar part of the entity (or complex S12) formed between both components of the mixture or by the DMF molecule. The Q-solvent interactions compete with homo- and heteromolecular solvent–solvent interactions.