The transport mechanism was investigated for n-butane, 1-butene, ethane, and ethene through anhydrous Ag+-doped PSM at various upstream gas pressures. 1-Butene and ethene molecules can be adsorbed and form multilayers on the Ag+ sites in the membrane. Their adsorption behavior can be described by the BET n-layer adsorption theory. These adsorbed alkene molecules can also swell the surrounding polymer chains to a certain extent, causing resistance to the migration of these alkene multilayer molecules to decrease as the concentration of the adsorbed alkenes increases. The permeation behavior of 1-butene and ethene is mainly controlled by the hydrodynamic surface flow mechanism, and their fluxes are much higher than those of alkanes, especially at high upstream gas pressures. This leads to the high ideal selectivity of 1-butene/n-butane and ethene/ethane at relatively high pressure. It is also shown that the more C atoms present in the hydrocarbon molecules, the higher will be the permselectivity of alkenes relative to their corresponding saturated alkanes, which will be expected in the anhydrous Ag+-doped PSM.