1 H-NMR spectra in binary mixtures of sulfolane with ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol have been recorded over the whole composition range at 303 K under atmospheric pressure. The experimental data have been used to calculate the deviations in chemical shifts from the additive properties, viz. Δδ, as a function of mole fractions, and values obtained are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.