A series of nine difunctional 1-propenyl ether monomers bearing ether, ester, carbonate, and urethane groups were prepared based on trimethylolpropane diallyl ether as the starting material. The monomers were fully characterized and then subjected to photoinitiated cationic polymerization using diaryliodonium salts as photoinitiators. The course of the polymerizations was followed using Fourier transform real-time infrared spectroscopy and the relative reactivities of the various monomers were determined. It could be shown that the differences in reactivity could be related mainly to the basicity of the functional group introduced into the molecule.