The reactions [Ru(NH3)5pz]2++S2O8(2-) and [Ru(NH3)5pz]2++[Co(C2O4)3]3- have been studied in solutions of 4-sulfocalix[4]arene sodium salt. Results show a binding of the ruthenium complex to the calixarene with a 2:1 stoichiometry; that is, a ruthenium molecule binds to two calixarene molecules. This stoichiometry changes when NaCl is added to the medium. Thus, a mixture of 1:1 and 2:1 adducts is found in the presence of 0.1 mol dm(-3) NaCl and only 1:1 adducts when the salt concentration is increased up to 0.3 mol dm(-3). Results show that the binding of the ruthenium complex to the calixarene is due to electrostatic and nonelectrostatic interactions. Kinetic data are interpreted by using the pseudophase model and taking into account the stoichiometry of the ruthenium binding to calixarene. The presence of a supporting electrolyte in the medium produces ion pair formation which exerts an influence on the kinetic rate constants.