A systematic study of the free radical photoinitiated alternating crosslinking copolymerizations of dialkyl maleates and furmarates with multifunctional vinyl ethers was carried out. The photocopolymerizations were fast and highly efficient when carried out using a variety of alpha-cleavage photo-initiators. The effects of the structures of the both the unsaturated esters and the vinyl ether monomers were examined. Dialkyl maleates were observed to be more reactive than the corresponding fumarate esters. The photopolymerization rates of several of these comonomer pairs were compared with standard diacrylate and dimethacrylate monomers. A range of different physical properties can be obtained by varying the length of the alkyl chain on alcohol portion of the unsaturated ester monomer. Prospects for the use of these comonomer systems in UV curable coatings, adhesives, printing inks, and composites are discussed. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4726-4736, 2010