Beta-(Vinyloxy)ethyl cinnamate (VEC) is shown to undergo living cationic polymerization, in the presence of EtAlCl2 and 1-(isobutoxy)ethyl acetate or trifluoroacetic acid and ZnCl2, probably via a mechanism similar to that of isobutyl vinyl ether (IBVE) polymerization. Some kinetic data for VEC polymerization are presented. The living PVEC cations polymerized IBVE to produce poly[beta-(vinyloxy)ethyl cinnamate]-b-poly(isobutyl vinyl ether) (PVEC-b-PIBVE). This diblock copolymer forms polymer brushes on glass plates and brush can be fixed by the photo-cross-linking of the PVEC block.