Chemical structure and morphology of polymers are directly related with the membrane separation performance. Poly(imide)s (PIs) are the most widely used polymers in the preparation of membranes for gas separation applications; thus, research on the structural design of polymers is of great interest to develop new membranes. In the present work, we reported the synthesis, characterization, and measurement of the gas transport properties of a new co-poly(imide)s (PI-D2a-D2b-6FDA) prepared from a mixture of isomeric diamines. The co-poly(imide) synthetic route involved several steps, starting by a bromination reaction, followed by a double nucleophilic aromatic substitution giving an isomeric mixture of precursors, which suffered a Suzuki-Miyaura C-C crosscoupling reaction followed by the reduction of nitro groups to give two new isomeric diamines. Finally, diamines simultaneously reacted with the dianhydride 6FDA to obtain PI-D2a-D2b-6FDA. The co-poly(imide) had a Mn of 47.7 kDa and a Mw of 74.0 kDa with a PDI of 1.6. The sample exhibited a 10% weight loss at 540 degrees C, Tg of 280 degrees C, BET surface area of 110 m2 g-1, and wide-angle X-ray diffraction (WAXD) interchain d -spacing at 9.5 & Aring; and 6.3 & Aring;. Tensile strength, elongation at break and Young's modulus were 109.6 MPa, 6.66% and 2.18 GPa, respectively. co-Poly(imide) was soluble in various polar aprotic organic solvents such as DMSO, NMP, DMF, DMAc, THF, and chloroform, forming a self -standing dense film whose gas transport properties were measured. Pure gas permeability coefficients for H2, CO2, O2, N2, and CH4, were 47.28, 24.04, 4.35, 1.02, and 0.76 (Barrer), respectively, which follows a decreasing order by the increasing kinetic diameters of the respective gases. Ideal gas selectivities H2/N2, O2/N2, CO2/CH4, and CO2/N2 were 46.4, 4.3, 31.6, and 23.6, respectively. These gas transport properties were compared with the commercial polymer Matrimid (R), showing higher gas permeability coefficients than Matrimid (R).