Separation of aromatic/aliphatic hydrocarbon mixtures by pervaporation has been of increasing interest in recent decades. Dozens of polymer materials have been reported for separations of benzene/cyclohexane and toluene/iso-ocatne mixtures. However, fundamental understanding of material structure and transport relations is not adequate to generalize guidelines for materials screening. The goals of this study are to tailor the structure of the polyimide materials, correlate the structure and transport relations, and establish guidelines for future materials. The 3, 5-Diaminobenzoic acid (DABA) containing polyimides were synthesized by both chemical and thermal solution imidization. The synthesized polyimides were formed into dense films by solution casting. The physical properties of the polyimides synthesized with monomers: 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4, 6-trimethyl-1, 3-phenylendiamine (DAM) and DABA, were characterized by DSC, WAXD, GPC and density. The chemical structures were assessed by FTIR and NMR. The pervaporation and sorption of the synthesized polyimide membranes were tested in toluene/iso-octane mixtures at 100°C. The structure- transport property relations were established for the 6FDA-DAM/DABA membranes. The 6FDA-DAM/DABA polyimides were crosslinked by ethylene glycol. The pervaporation and sorption of the crosslinked membranes were tested in toluene/iso-octane mixtures at 100°C. Thermal imidization was found to give a higher imidization degree than chemical imidization. As a result, the polyimides made by chemical imidization contain a higher percentage of carboxylic acid groups than those made by thermal imidization. Chemical imidization gives higher film density, glass transition temperature and lower flux and higher selectivity for the toluene/iso-octane pervaporation than the thermally imidized membranes because of the higher carboxylic acid concentration. The chemically imidized membranes are slightly brittle after the crosslinking. Only the thermal imidization membranes have good flexibility and its pervaporation selectivity improves significantly after the crosslinking. Solubility selectivity and diffusivity selectivity of the 6FDA-DAM/DABA membranes were correlated with solubility parameters and fractional free volume, respectively. The structure-mass transport relations show that for the 6FDA-DAM/DABA membranes, both solubility selectivity and diffusivity selectivity contribute to the pervaporation selectivity. For the chemically imidized membranes, increased DABA concentration has a positive effect on solubility selectivity and diffusivity selectivity. For the thermally imidized membranes, increased DABA concentration has a significant effect on diffusivity selectivity only. / text