High molecular weight poly(imide-amides) can be readily formed by the palladium-mediated carbonylation and condensation reactions of activated chlorophthalimide monomers and aromatic diamines. The presence of iodide ion greatly accelerates the rate of reaction and increases the ultimate molecular weight of the polymer. Polymerizations proceed best using a protocol of high CO pressure (90 psig) for 2-4 h, followed by lower CO pressure (20 psig) in DMAc or NMP for 24-48 h at 100 degrees C using 0.3-3.0% PdCl(2)L(2) (L = PPh(3)) as the catalyst with 2-6 equiv of PPh(3)/Pd and 0.3-1.0 equiv of an iodide/chloro group.