A series of rhenium containing polyimides was prepared by the polymerization between a tri-carbonylrhenium diimine complex with various aromatic dianhydrides. Electronic absorption spectra of the polymers showed a very strong intramolecular charge transfer transition which obscures the transfer transition band due to the rhenium complex in the visible region. A large photocurrent response was also observed when the polyimide was irradiated at 514 nm.