Abstract: We considered the physicochemical regularities and analytical capabilities of separation methods based on the manifestation of capillary effects in hydrophobic microporous media, namely, liquid–gas chromatography with a stationary gas phase in the pores of a solid-phase substrate and a mass-exchange process in liquid–gas and liquid–liquid systems, carried out in a biporous matrix. The advantages of these methods compared to conventional mass-exchange processes in the same systems in terms of higher efficiency and a possibility of the separation of substances in a continuous mode are shown.