An important consequence of the interaction of calix(n)arenes and amines is the generation of new electrolytes resulting from proton transfer reactions from the calix(n)arene molecule to the amine. A brief account on the contributions made in this area is presented. This is followed by recent electrochemical (conductimetric and potentiometric) and thermodynamic studies on the interaction of a phenol-based-calixarene and amines in non-aqueous media. The thermodynamics of extraction of amines by p-m butyl calix(8)arene in the water-benzonitrile solvent system is discussed taking into account the parameters which contribute to the overall process. The results obtained from conductimetric and spectrophotornetric studies on the interaction of a resorcinol-based calixarene and amines are presented.