A composite membrane for selectively separating (e.g., pervaporating) a first fluid (e.g., first liquid such as a high octane compound) from a mixture comprising the first fluid (e.g., first liquid such as a high octane compound) and a second fluid (e.g., second liquid such as gasoline). The composite membrane includes a porous substrate comprising opposite first and second major surfaces, and a plurality of pores. A pore-filling polymer is disposed in at least some of the pores so as to form a layer having a thickness within the porous substrate. The composite membrane further includes at least one of: (a) an ionic liquid mixed with the pore-filling polymer; or (b) an amorphous fluorochemical film disposed on the composite membrane.