Demicellization of a 90 mM sodium dodecyl sulfate (SDS) solution in water at 10, 22, and 30 °C was studied by isothermal titration calorimetry (ITC). ΔH of the demicellization process was strongly temperature dependent, having an exothermic progression (-20.4 ± 0.9 kJ∕mol, max) at 10 °C and an endothermic one (3.7 ± 1.2 kJ∕mol, max) at 30 °C. ΔH for micelle dilution followed a slightly endothermic progression (0.9 ± 0.5 kJ∕mol at 30 °C, 0.7 ± 1.3 kJ∕mol at 22 °C, and 0.0 ± 0.5 kJ∕mol at 10 °C) at all studied temperatures. No differences in ΔH for micelle dilution and demicellization was observed at 22 °C. The temperature dependence of ΔH measured by ITC could be related to hydrophobic interactions. Therefore, ITC was shown to be a useful tool to describe the thermodynamics of demicellization processes and in addition to determine alterations in ΔH caused by changes in hydrophobic and steric∕electrostatic interactions.