The counter-diffusion of two gaseous substances permeating a polymeric membrane has been investigated both experimentally and theoretically. The aim of the study was to find mutual effects, if any, that could influence the permeability and diffusivity data. The experimental data were obtained with an isostatic permeameter operating at ambient pressure and 303 K: helium, nitrogen, carbon dioxide methane were used as permeating gas at different partial pressure; helium or nitrogen as equilibrating or carrier gas. No evident mutual effect of the counter-diffusing gas was observed. The theoretical analysis gave some insight into the phenomena and it was concluded that at near-atmospheric pressures, and in the absence of swelling phenomena no mutual interaction exists. On a theoretical basis any mutual interaction between diffusing and counter-diffusing gases could only occur: i) at high pressures , when the free movement of permeating gas molecules within the polymer is hindered by the counter-diffusing gas; ii) when a large part of the free volume fraction is occupied by the counter--diffusing gas; iii) swelling phenomena modify the structure and free volume fraction of the polymer.