Addition of Cp*TiMe(3) and B(C6F5)(3) (1:1 ratio; Cp* = eta(5)-pentamethylcyelopentadienyl) to toluene or methylene chloride solutions of N-vinylcarbazole or the vinyl ethers CHR’CHOR " (R’ = H, R " = Me, Et, CH(2)CHMe(2); R’ = Me, R " = Et) and 2,3-dihydrofuran at room temperature or -78 degrees C results in the formation of polymers which generally exhibit unusually high molecular weights and narrow molecular weight distributions. The materials, which are formed via carbocationic initiation by the titanium-containing cationic complex [eta(5)-C(5)Me(5))TiMe(2)](+) rather than via Ziegler-Natta processes, are in all cases characterized by GPC and C-13{H-1} and (1)NMR spectroscopy, some by DSC and IR Spectroscopy. The neutral borane, B(C6F5)(3), is also a carbocationic polymerization initiator, but is generally less active than the titanium-containing cation.