Based on the Grubbs 2nd catalyst, several creative Grubbs 3rd catalysts were synthesized by reaction with pyridine ligands of different types. The structures were characterized and confirmed by 1H NMR. The bulk polymerization of dicyclopentadiene was catalyzed by the newly synthesized G3 catalysts. On the basis of controllable polymerization by adding triphenylphosphine polymerization inhibitor, polydicyclopentadiene material was prepared by mould casting method. The effects of polymerization inhibitor, different catalysts and different catalyst contents on the properties of polydicyclopentadiene material were discussed. The structure was characterized by FT-IR, TGA and DSC. p-DCPDThe results indicate the introduction of PPh3 could prolong the spot life of DCPD mixed solution with Grubbs 3rd catalysts more significantly than that with Grubbs 2nd catalyst. The newly synthesized Grubbs 3rd catalysts exhibited excellent catalytic performance for DCPD polymerization, obviously improving the mechanical properties of p-DCPD materials. Moreover, the p-DCPD manufactured from benzomethylene-[1,3-bis(trimethylphenyl)-2-imidazoline subunit]-dichloro-bis(3-methylpyridine) ruthenium（G3-5） exhibited better performance thermal stability and compact cross-linking structure.