Polymerizable tetrachloro-perylenediimdes containing endo/exo-norbornene groups on both imide sides were designed and synthesized. Endo/Exo-type soluble ladder-like polynorbornenes with perylenediimide (PDI) as bridges were prepared by ring-opening metathesis polymerization (ROMP). XRD characterizations showed that the ladder-like polynorbornenes had ordered structures similar to the supramolecular precursors assembled from the corresponding monomers. TGA measurements demonstrated great thermal stabilities for the both target P1-Endo and P2-Exo with Td of about 320 degrees C at 5 wt % loss, respectively, which is important for further application in devices. Both polymers have good solubility in common organic solvents and easy to form thin films. Photophysical studies and cyclic voltammetry investigations reveal that polynorbornene films have wide-range absorption from 400 nm to 600 nm and the HOMO/LUMO energy levels could be matched well with the donor-PCzTh-TVDCN. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012