The importance of Doxorubicin (Dox) as anti-cancer drug is well recognized. Dox side effects are however a major drawback in an efficient medicinal utilization. Cyclodextrin inclusion is an effective approach to enhance drug delivery and stability. In this research host - guest complex formation of Dox cytotoxic drug with gamma-cyclodextrin (gamma CD) in aqueous solutions and in solid state was investigated by differential scanning calorimetry (DSC), thermogravimetry (TG), Fourier transform infrared spectroscopy (FT-IR) analysis, scanning electron microscopy (SEM), ultraviolet-visible (UV-vis) spectroscopy, isothermal titration calorimetry (ITC) and pH measurements. The thermodynamic parameters were discussed considering the weak interactions between gamma CD and Dox molecules. UV vis and ITC gave comparable results regarding the formation constant and thermodynamic parameters values. The data indicated that the gamma CD/Dox complex in the aqueous solution is formed in a 1:1 stoichiometry ratio and the binding process of gamma CD with Dox is exothermic and enthalpy controlled, but entropy driven. The solid state characterization of the gamma CD/Dox complex indicated the occurrence of complexation by encapsulation of the hydroxyanthraquinonic rings of Dox into gamma CD cavity and come to support and complete the data resulted from liquid state investigation.