Two methods for synthesizing thin films of chemically selective polymers onto the surfaces of microporous hollow-fiber membranes are described. The first involves interfacial redox polymerization and yields thin films of electronically conductive polymers (e.g., polypyrrole, poly(N-methylpyrrole), polyaniline) on the outside surface of the hollow-fiber membrane. The second method entails interfacial photopolymerization of styrenic monomers on the surface of the hollow-fiber membrane. Such coated hollow-fiber membranes are potentially useful in membrane-based separation technologies such as pervaporation and industrial gas separations. We also investigated the transport properties of the coated hollow-fiber membranes described here using a simple pervaporation-type experiment.