For the membrane-based separation of benzene/cyclohexane mixtures, the pervaporation properties of different 6FDA (4,4'-hexafluoroisopropylidene diphthalic anhydride) based copolyimide membranes have been investigated. In order to obtain high permeability as well as high selectivity copolyimides were synthesised using a combination of 4MPD (2,3,5,6-tetramethyl-1,4-phenylene diamine) and 6FpDA (4,4'-hexafluoro-isopropylidene dianiline) as well as DABA (3,5-diaminobenzoic acid) as monomers. Cross-linking is possible with this type of copolyimides and necessary to reduce swelling effects, which often occur with polymeric membranes and lead to a deterioration of the separation characteristics in aromatic/aliphatic separation processes. In order to find the most suitable membrane material, the polymer structure, the crosslinking agents, as well as the crosslinking methods have been varied. The separation characteristics have been determined by sorption and pervaporation experiments. Sorption experiments have been carried out at 60 degrees C using benzene, toluene and ethylbenzene as aromatic components and cyclohexane, cyclohexene, hexane and heptane as aliphatic solvents. Pervaporation experiments have been performed at 60 degrees C using benzene/cyclohexane mixtures with benzene concentrations covering the whole concentration range. It has been found that crosslinked copolyimide membranes show excellent chemical resistance, strongly reduced swelling behaviour and higher selectivity in aromatic/aliphatic separation compared to conventional membrane materials.