A review is presented for various gas transport mechanisms through microporous membranes of both polymeric and inorganic materials. Different transport modes manifest depending on the pore size and the flow regime, which is a function of pressure, temperature, and the interaction between gas molecules and the pore walls. For microporous membranes whose pores are small and the internal surface area huge, the surface diffusion becomes a significant factor. If the pores become even smaller, then the transport mechanism will be more of an activated diffusion type. When conditions are right capillary condensation will take place to create an enormous capillary pressure gradient, which will greatly enhance the permeation flux. At the same time the capillary condensate of the heavier component may block the membrane pores denying the passage of the lighter gas molecules. All of these phenomena will influence the separation of mixtures.