Abstract Aqueous solutions containing sugar-based surfactants, alkyl glucosides, thioglucosides and maltosides, have been investigated in a wide concentration range, at different temperatures. Colligative properties (freezing point and vapour pressure depression), volumetric, adiabatic compressibility, surface tension and calorimetric methods were used. The results give information on the Gibbs energy of transfer from water to a micellar environment and on other thermodynamic contributions to the overall aggregate stability. The thermodynamic quantities derived from the above experimental methods were interpreted by taking into account the role of polar head groups in modulating micelle formation. Use of a mass action approach allows determining micelle aggregation numbers, 〈N〉, from partial molal quantities. The differences between values obtained from calorimetric, colligative, compressibility, surface and volumetric properties were rationalised on proper grounds.