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It is interesting to see the nature of intermolecular interactions between associative and non-associative polar liquids. Binary polar–polar liquid mixtures of ethyl acetate, ethyl benzoate, ethyl acrylate, ethyl butyrate, n-butyl acetate and benzyl benzoate, each with propanoic acid were subjected to dielectric studies at temperatures 25 °C, 35 °C and 45 °C. Static permittivity (ε_o) and dielectric constant at high frequency (ε_∞) were found through dielectric measurements for different concentrations of each system. The Bruggeman dielectric factor, Kirkwood correlation factor and the excess permittivity were determined. Deviations from the linearity of various models suggest molecular association through hydrogen bonding between the polar–polar constituents of the mixtures. The formation of cyclic and linear α-multimers in the above systems were identified. The results and their temperature dependence were interpreted …