We synthesized new polynorbornene dicarboximide (PCaNI) functionalized with hole-transporting carbazole moieties and its copolymer (PCaNA) by ring-opening metathesis polymerization (ROMP), where the PCaNA was further reacted with 3-amino-triethoxysilane to prepare PCaNI/silica hybrid. We also investigated the feasibility of PCaNI and PCaNI/silica hybrid (PCaSi) as a hole-transporting material for hybrid organic light emitting devices (HOLEDs). To improve the performance of the PCaNI-based HOLEDs, N, N '-diphenyl-N, N '-(3-methylphenyl)[1,10-biphenyl]-4-4 '-diamine (TPD) was also introduced into the PCaNI matrix. Results showed that PCaNI exhibited high glass transition temperature (similar to 260 degrees C) and high optical transparency in the visible region. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of PCaNI were measured as 5.6 and 2.2 eV, while the TPD-doped PCaNI showed 5.7 eV (HOMO) and 2.6 eV (LUMO). The PCaNI/silica hybrid nanolayers showed excellent solvent resistance due to the formation of covalent bonds between ITO and PCaNI. The HOLEDs with PCaNI/TPD or PCaSi/TPD hybrid nanolayers exhibited relatively higher luminance (similar to 10,000 cd/m(2)), lower operating voltage (similar to 6.5 V at 300 cd/m(2)), and higher current efficiency (similar to 2.7 cd/A). (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5189-5197, 2010