The thermodynamic parameters viz. excess molar volume V-E and ultrasonic velocity u, transport parameter viscosity n and spectroscopic parameters viz. IR, 'H and C-13 NMR have been measured for the mixtures of alpha,omega-alkanediols (1,2- ethanediol, 1,3-propanediol, and 1,5-pentanediol) and NN-dimethylformamide over the whole composition range at T = 308.15K. The partial molar quantities Q(i)(E), isentropic compressibility Ks, deviation in ultrasonic velocity a, viscosity deviation Art, deviation in Gibbs free energies of activation for viscous flow g(x) and excess NMR chemical shift delta(E) have been estimated and analysed. The results reveal distinctly that the interaction between unlike molecules takes place through hydroxyl groups of a,w-alkanediols and the > CO group of N,N-dimethylformarnide. An excellent correlation between thermodynamic and spectroscopic measurements has been observed. (C) 2006 Elsevier Ltd. All rights reserved.