Mixing of oppositely charged surfactants and polyelectrolytes in aqueous solutions leads to cooperative surfactant adsorption onto the polyelectrolyte chains. Experimental determination of surfactant/polyelectrolyte binding isotherms is usually done using custom-built surfactant-ion-specific electrodes. As an alternative, we present an indirect isotherm approximation method that uses conventional isothermal titration calorimetry (ITC). The calorimetric data is fitted to the two-binding-state Satake-Yang adsorption model, which quantifies the extent of binding in terms of the binding constant (Ku) and the cooperativity parameter (u). This approach is investigated using two surfactant/polyelectrolyte mixtures: sodium perfluorooctanoate (FC7) and N,N,N-trimethylammonium derivatized hydroxyethyl cellulose (UCARE Polymer JR-400), whose binding behavior follows the Satake-Yang model, and dodecyltrimethylammonium bromide (DTAB) and poly(styrenesulfonate) (NaPSS), whose behavior deviates dramatically from the Satake-Yang model. These studies demonstrate that, in order to apply the indirect ITC method of binding isotherm determination, the surfactant/polyelectrolyte adsorption process must have no more than two dominant binding states. Thus, the technique works well for the FC7/JR-400 mixture. It fails in the case of the DTAB/NaPSS adsorption, but its mode of failure offers insight into the multiple-binding- state adsorption mechanism.