Treatment of ruthenium-vinylcarbene complex[Ru(CHC(PPh₃)CH(2-Py))Cl₂PPh₃]BF₄ (1) and PPh₃ with nucleophilic reagents H₂O, CH₃OH, NH₂Ph, or 2-mercaptopyridine led to the ruthena-polycyclic complexes[Ru(CHC(PPh₃)-CHR(2-Py))Cl(PPh₃)₂]BF₄[R=OH (2), R=OCH₃ (3), R=NHPh (4)] or[Ru(CHC(PPh₃)CH(S(2-Py))(2-Py))PPh₃-(S(2-Py)]BF₄ (5). They are stable under air at solid state. CH₃OH in the reaction is not only the reagent but also the solvent and the reaction must be heated at 60 ℃ for 6 h. All the other reactions were carried out at room temperature in CH₂Cl₂. The crystals of 4 and 5 were grown from CH₂Cl₂ and CHCl₃ solutions layered with diethyl ether, respectively. The structures 4 and 5 were determined by X-ray crystallography. The crystal size of 4 is a=1.29145(3) nm, b=1.37687(5) nm, c=1.86914(4) nm, α=92.114(2)°, β=106.271(2)°, γ=96.333(3)° and the size of 5 is a=1.15333(18) nm, b=1.20072(19) nm, c=1.9081(3) nm, α=88.466(3)°, β=87.918(3)°, γ=79.521(3)°. In addition, refluxing 1 with PPh₃ in CHCl₃ for 6 h to produce red solid[Ru(CHC(PPh₃)CH(2-Py))Cl₂(PPh₃)₂]BF₄ (6). The reaction of complex 6 with HBF₄ at room temperature for 3 h afforded the (μ-Cl)₃-bridged bisruthenium-vinylcarbene complex[{Ru(CHC(PPh₃)CH(2-Py))PPh₃}₂(μ-Cl)₃](BF₄)₃ (7) in 87% yield. The crystal of 6 was grown from CH₃COCH₃ solution layered with diethyl ether, and the crystal of 7 was grown from CHCl₃ solution layered with diethyl ether. The structures of 6 and 7 were also determined by X-ray crystallography. The crystal size of 6 and 7 are a=1.13777(3) nm, b=1.56466(7) nm, c=1.79541(7) nm, α=75.822(3)°, β=79.502(2)°, γ=79.259(3)°, a=1.68830(3) nm, b=2.33421(4) nm, c=2.48603(4) nm, α=90°, β=96.5530(10)°, γ=90°, respectively. The CCDC number for 3, 5, 6, and 7 are 945539 (3), 945538 (5), 945541 (6), and 945542 (7). All these complexes were fully characterized by elemental analysis and NMR spectroscopy.