We have designed and synthesized novel perfluorinated polyimides with 3D controlled structure. At first, we successfully developed the new synthetic routes to diamines with pendant bulky perfluorinated aromatic units in a multi-step synthetic procedure. Novel perfluorinated polyimides were prepared in a two-step reaction in N-methyl-2-pyrrolidinone (NMP) solution: The first step was for the synthesis of polyamic acids (PAAs) and the second reaction was for the imidization of PAA. The polymer yield was over 89% and the inherent viscosity of PAAs was in the range of 0.24-0.36 dL/g. The thin films were prepared by spin-coating the PAA solution in NMP onto various substrates such as a Si wafer or a KBr pellet, dried at 80 degrees C and further cured at 230 degrees C. The resultant polyimides are thermally stable over 400 degrees C. The refractive index and birefringence of the resultant polyimides are 1.5858-1.6452 and 0.01-0.005, respectively. The refractive index of polyimide decreases with increasing the fluorine content. The copolymerization and the ether linkages into the backbone reduce the birefringence of polyimides. Surprisingly, the pendant ether linkage is not a crucial factor in reducing the polyimide birefringence. Their birefringence is comparatively very low, compared with that of previous polyimides. (c) 2005 Wiley Periodicals, Inc.