Convective drying is the most widely used technique to stabilize by-products in the food industry, permitting later processing. A thorough knowledge of the relationship between moisture content and water activity allows the optimization of not only drying operations, but the settings of storage conditions. Thus, the thermodynamic properties of pomegranate peels were determined during the desorption process. Experimental sorption isotherms at 20, 30, 40 and 50 °C showed type II Brunauer behavior. Eight different theoretical and empirical equations were fitted to the experimental results; the theoretical GAB model and the empirical Peleg model were the ones that achieved the best fit (R2 of 0.9554 and 0.974, respectively). The Clausius–Clapeyron equation and the enthalpy–entropy compensation theory were used to determine the thermodynamic parameters. The isosteric heat determined from the sorption isotherms decreased regularly as the equilibrium moisture content rose (from 8423.9 J/mol at 0.11 kgH2O/kg d.m. to 3837.7 J/mol at 0.2 kgH2O/kg d.m.). A linear compensation was observed between enthalpy and entropy, which indicated an enthalpy-controlled sorption process.