A novel pentamethylated norbornadiene (NBD) based dianhydride, alpha, alpha'-bis-(3,4,5,6,7-pentamethylcyclopenta-2,4-dienyl)meta-xylene-1,2-d ianhydride (3), was prepared from alpha, alpha'-bis-(pentamethylcyclopentadienyl)meta-xylene (1) and acetylene dicarboxylic acid. The bis-adduct formed via Diels-Alder reaction afforded tetra-acid (2), which was chemically cyclode-hydrated to lead the targeted dianhydride (3). New polyimides containing NBD moieties in the main chain were prepared from the dianhydride monomer (3) and various aromatic diamines. The chemical structure of the polymers was confirmed by both H-1 and C-13 NMR analysis. Their Molecular weights were also measured by SEC. All of these polyimides are soluble at room temperature in common organic solvents, such as chloroform, dichloromethane, THF, DMSO, DMF, and NMP, and show good thermal stabilities. The photochemical isomerization of the NBD into quadricyclane (QC) was investigated by UV/vis spectrophotometry from polymer films using visible sunlight as irradiation source. It was found that the kinetic rate of the conversion NBD-QC which proceeded smoothly is a first kinetic order. The stored energies released by the transformation of QC groups into NBD ones of the irradiated polymer films were also evaluated by DSC measurement and were found to be around 90 kJ mol(-1). (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1988-1998, 2011