The eight-membered cyclic monomer, prepared by Diels-Alder reaction of 1,5-cyclooctadiene and anthracene, polymerized via Ru-catalyzed ring-opening metathesis to efficiently afford high polymers (M-n up to 631,000). Unsaturated moieties in the main chain of the obtained polymer were hydrogenated with a homogeneous ruthenium catalyst in quantitative conversion, confirmed by H-1-NMR measurement. The self-standing membranes were provided by casting the tetrahydrofuran solutions of both nonhydrogenated and hydrogenated polymers. The obtained membranes showed high transparency in the region of >300 nm with mechanical flexibility. Thermal gravimetric analysis revealed that both nonhydrogenated and hydrogenated polymers decomposed in two stages. The first-stage decomposition starting at around 230 degrees C was caused by retro Diels-Alder reaction forming anthracene, proven by pyrolysis gas chromatography mass spectroscopy (GC-MS) analyses. Mechanical grinding of the polymers induced the formation of anthracene in solid state, which transformed the polymer into blue-luminescent materials under UV irradiation. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1392-1400