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Recently, porous membranes have attracted substantial attention to be used for membrane gas absorption. Existing industrial technologies lack membrane contactors able to function under elevated pressure and/or with organic liquids, because liquid absorbent penetrates into membrane pores causing pore wetting and drastic mass exchange characteristics decrease. This work is focused on development of novel porous asymmetric hollow fiber membranes having mesoporous skin layer and controlled hydrophilic/hydrophobic surface properties for gas-liquid membrane contactors able to function in aqueous media as well as in organic liquids under elevated pressure. Polysulfone (PSF) was used because it is an excellent material for spinning hollow fiber membranes with controlled pore sizes. Hollow fiber membranes have been prepared by the dry-wet phase-inversion technique followed by membranes surface chemical modification. Membranes were characterized by means of gas permeability, scanning electron microscopy, contact angle etc. Liquid hydrocarbon (hexane) permeation through virgin and modified membranes was studied as well. Hollow fiber membranes modified by perfluorinated acrylic copolymer (Protect Guard®) showed resistance to organic liquid penetration under the transmembrane pressure up to 1 bar. This makes them promising for employing in gas-liquid membrane contactors. To our best knowledge, this is a first example of PSF-based porous hollow fiber membrane suitable for gas-organic liquid contactors.