A new approach for preparation of multifunctional polymers with pendant vinyl ethers was investigated. In particular, 2-(l-propenyl)oxyethyl methacrylate, a new ambifunctional monomer combining easy radical polymerization and a fast cationically cross-linkable group, was evaluated. Hence, the physical characteristics of copolymers were controlled by the selection of comonomers. Cross-linking kinetics as a function of temperature and concentration of the acid-generating species were monitored quantitatively by FT-IR spectroscopy. Through the use of DSC measurements, the onset for cationic polymerization was determined. It was demonstrated that both 9-fluorenylideneimino-p-toluenesulfonate and diphenyliodonium triflate could be used as efficient thermally initiating cross-linking agents.