1-Butenyl glycidyl ether was prepared in high yield by the ruthenium-catalyzed isomerization of crotyl glycidyl ether. This ambifunctional monomer underwent facile photoinitiated cationic polymerization using diaryliodonium salts as photoinitiators. The progress of the polymerizations was followed using Fourier transform real-time infrared spectroscopy, and the reactivity of this monomer under various experimental conditions determined. A comparison of the rates of polymerization of the epoxy and vinyl ether groups suggested that the polymerization may take place by an intramolecular cyclization process that generates cyclic acetal units in the backbone of the polymer. It was further shown that crotyl glycidyl ether undergoes regioselective cationic ring-opening polymerization to give a polyether, and then isomerization was carried out to give an oligomer bearing reactive pendant 1-butenyl ether groups.