The $pi$-complex membranes of poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) of two silver salts of $AgBF_4$ and $AgCF_3SO_3$ were prepared and tested for the separation of the propylene/propane mixtures. The Fourier-transform infrared (FT-IR) spectra of these complexes showed that the silver salts were dissolved in SEBS up to a silver mole fraction of 0.14, due to $pi$-complexation between the aromatic C=C bonds of styrene blocks and silver ions. Above this solubility limit, ion pairs and high-order ionic aggregates began to form, so that silver salts were distributed unselectively in both the EB and PS blocks. The domain size of the PS blocks was enlarged up to this critical concentration with increasing silver concentration without structural transitions, as confirmed by small angle x-ray scattering (SAXS). These structural properties of the SEBS/silver salt complexes may explain the lower separation properties for propylene/propane mixtures compared to poly(styrene-b-butadiene-b-styrene)(SBS)/silver salt complex membranes.