The use of ±2,2'-diamino- 1,1'-binaphthalene as a monomer for the synthesis of soluble, microporous poly(imide) has been reported. Polyimides were prepared by two different pathways with a one-step route, employing m-cresol as solvent and isoquinoline as catalyst and were dissolved in m-cresol in equal amounts under a N2 atmosphere. Microporous, purely organic materials gained increasing interest during the past years as they have a high potential in a variety of applications like gas separation or storage. The resulting polymers were soluble in CHC13, DM50, NMP, THF, DMAc, and DMF. The resulting polyimide showed, contrary to other polyimides, good solubility in a broad variety of organic solvents, which can be attributed to its contorted structure which suppress easy, space-efficient packing.