The 5-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximido) isophthalic acid (DEAIA) monomer, containing a dibenzobarrelene pendant group, was synthesized by the condensation of 5-aminoisophthalic acid and 9,10-dihydroanthracene-9,10-α,β-succinic anhydride (DASA). The DEAIA monomer was reacted with four structurally different aromatic diamines to synthesize four novel polyamides. All aromatic polyamide based in the DEAIA monomer showed very good solubility in aprotic polar solvents and excellent thermal stability with onset of decomposition at 430 °C. They readily form membrane by the casting method. Moreover, the most interesting polyamide was DEAIA-6F that showed high thermal stability, good film formation, and the largest gas permeability coefficients in comparison with a reported polyhexafluoroisophthalamide, HFAISO; this confirms the advantage of inserting a dibenzobarrelene pendant group.