Novel cyclic olefin polymers (COPs) derived from bulky cyclic olefin, exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-1,4-methanoanthracene (HBMN), with high glass transition temperature (T-g), excellent thermal stability, high transparency, and improved mechanical performance, have been achieved by ring-opening metathesis polymerization and subsequent hydrogenation. The "first-generation Grubbs" catalyst, RuCl2(P-Cy-3)(2)(CHPh) (Cy = cyclohexyl) (G1), displays very high activity for homo/copolymerization with complete conversion. Homopolymer of the HBMN after complete hydrogenation showed a highest T-g of 223.6 degrees C. Copolymerization of HBMN with tricyclo[4.3.0.12,5]deca-3-ene or 5-n-hexylnorbornene was also carried out. These two series of COPs were characterized by gel permeation chromatography, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. The T-g of the resulted COPs linearly increased with HBMN content, which is easily controlled by changing feed ratios. The tensile test indicates that these copolymers have good mechanical performance as all these copolymers show a higher strain at break compared with commercial products (TOPAS (R)). (C) 2014 Wiley Periodicals, Inc.