Pervaporation (PV) performance of polyimide (PI) membranes has been attempted for the recovery of high concentrations of aprotic solvents, such as N, N-dimethyl formamide (DMF) and N, N-dimethylacetamide (DMAc). In this work, we explored the effect of chain structure on the solvent resistance and pervaporation performance of hydrophilic pyromellitic dianhydride (PMDA) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) based polyimide membranes. According to the Hansen solubility parameters and membrane formation morphologies, we selected five aprotic solvent resistant PI membranes with different chain structures. It was found that the swelling degrees in DMF and DMAc was principally determined by the elasticity modulus of the PI membrane, and was significantly influenced by the polymer chain structure. The flexible linkages (such as -O-CH2- and -CH2-) suppressed the PI chain packing, which resulted in the d-spacing and fractional free volume (FFV) of PMDA based PI membrane was higher than BTDA based PI membrane. BTDA-BZD membrane had the highest elasticity modulus together with the lowest d-spacing value (4.68 angstrom) due to its symmetric intermolecular interaction and rigid chain structure. PV experiments were conducted with DMF/water and DMAc/ water mixtures over a wide range of temperatures (30-60 degrees C) with 90 wt% solvent concentration. The BTDA based PI (M4) composite membrane showed the highest separating factor around 275 at 30 degrees C in DMAc solution, which was much higher than in DMF solution (the separating factor is about 70). Furthermore, the chemical and thermal stability WA for the PI composite membranes in the presence of the feed solvent under the PV process demonstrated the excellent separation stability in DMAc solution.