A series of dianhydride monomers, 2,2′-disubstituted-4,4′,5,5′-biphenyltetracarboxylic dianhydride (substituents = phenoxy, p-methylphenoxy, p- tert-butylphenoxy, nitro, and methoxy) were synthesized by the nitration of an N-methyl protected 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and subsequent aromatic nucleophilic substitutions with aroxides (NaOAr) or methoxide. These dianhydrides were polymerized with various aromatic diamines in refluxing m-cresol containing isoquinoline to afford a series of aromatic polyimides. The effects of varying 2,2′-substituents of the dianhydride (BPDA) moiety on the properties of polyimides were investigated. It was found that polyimides from the dianhydrides containing phenoxy, p-methylphenoxy, and p- tert-butylphenoxy side groups possessed excellent solubility and film forming capability whereas polyimides from 2,2′-dinitro-BPDA and 2,2′-dimethoxy-BPDA were less soluble in organic solvent. The soluble polymers formed flexible, tough and transparent films. The films had a tensile strength, elongation at break, and Young’s modulus in the ranges 102–168 MPa, 8–21%, 2.02–2.38 GPa, respectively. The polymer gas permeability coefficients ( P) and ideal selectivities for N 2, O 2, CO 2 and CH 4 were determined for the –OAr substituted polyimides. The oxygen permeability coefficient ( P O2) and permselectivity of oxygen to nitrogen ( P O2/N2) of the films were in the ranges 3.4–11.3 barrer and 3.8–4.6, respectively. The gas permeability typically increased with increasing free volume in the order of tert-butylphenoxy substituted PI > methylphenoxy substituted PI > phenoxy substituted PI.