Herein, the cloud points (CPs) of tween 80 (Tw 80) in water/(water + diols [ethanediol, propanediol, and butanediol])/(water + polyols [glucose, fructose, and sorbitol]) systems were measured. For diols‐Tw 80‐water system and polyols‐Tw 80‐water system, the CP values were obtained to reduce gradually with increasing content of diols and polyols at a particular concentration of Tw 80. For a certain concentration of Tw 80 having different contents of diols, the observed ∆H0c, as well as ∆S0c values, were negative over the range of concentration of diols studied, and the negative values of ∆H0c and ∆S0c were reduced with the enhancement of the content of diols. The values of ∆H0c were negative, which indicate the process was exothermic. The clouding process of Tw 80 in the presence of different diols is mainly enthalpy‐controlled process, while the contributions of enthalpy tend to reduce with enhancing of the contribution of diols. In the case of polyols‐Tw 80 mixture in an aqueous environment, the ∆Gc0 values were achieved positive. The values of ∆Hc0 and ∆Sco were obtained negative for studied systems, while the negative values reduce with enhancing of polyol (glucose and fructose) concentrations. For sorbitol‐Tw 80 system, the values of ∆Hc0 were observed to be negative and the negative magnitudes reduce with enhancing of sorbitol concentrations. The thermodynamic parameters of transfer are also evaluated and illustrated in detail.