A kinetic study of the joint homogeneous-heterogeneous catalysis for the quaternization of silver (I)-coordinated triethylamine and tributilamine by ethyl iodide was performed in toluene. The data obtained substantiated the superficial molecular arrangement, previously proposed by Barbosa and Spiro, and exposed a new competitive reaction of the non-coordinated soluble silver salt with the alkyl halide in the solvent under study. Estimates of the solution rate constants were obtained for both systems and evidence of a surface effect is also presented.