Preparation of a macromolecular monomer of a lactone allows the preparation of copolymers of lactones with commonly available olefinically unsaturated monomers. There is no known method for the preparation of such copolymers. A cationic ring-opening polymerization of a lactone in conjunction with an unsaturated alcohol (propagator) having an acryloyl, allyl or styryl double bond, produces a polylactone macromer having an ethylenic double bond at one end and a hydroxyl group at the other. The polymerization proceeds by polyaddition of the lactone to the OH group which is the propagating species. The polylactone may include a polymeric or non-polymeric spacer. The propagator is a primary or secondary alcohol which, if cyclic may have a single internal double bond in one ring. The catalyst is an oxonium salt, or etherate of boron trifluoride. The macromer may be copolymerized with a wide variety of olefinically unsaturated monomers to form a macromer copolymer with pendant polylactone chains. In particular, block copolymers of terminally unsaturated macromers of ether-ester, or ester-ether structure may be tailored for specific applications.