The association between α-cyclodextrin and three monoalcohols (1-pentanol, 1-hexanol, and 1-heptanol) in (glycerol + water) was studied by titration microcalorimetry at T = (288. 15, 298.15, and 308.15) K. The apparent thermodynamic parameters for the binding reactions, the equilibrium constant K (obs) and enthalpy of reaction r H o m (obs), were calculated from the calorimetric results. Knowing from a prior study that glycerol associates with α-cyclodextrin in aqueous solution, the observed values were corrected for this equilibrium, assuming as a model that there is identical linkage. The intrinsic values of the thermodynamic parameters for the binding reaction, K (int) and r H o m (int), were then calculated for the three studied temperatures. From these values, the change in Gibbs free energy and entropy upon binding, r G o m (int) and r S o m (int), respectively, were also calculated. From the temperature dependence of the enthalpy changes, the change in heat capacity for the binding reactions r C o p,m was obtained. The values of the intrinsic thermodynamic parameters are compared with the corresponding ones in water. For all compounds and temperatures, there is an increase in binding strength, as reflected by higher K values. The fact that the intrinsic parameters have different values from the ones observed in water shows that the glycerol linkage to the monoalcohols binding to α-cyclodextrin explains just part of the change in the observed parameters, indicating that glycerol is also acting as a co-solvent, thus affecting the solution interactions.