Fumarate esters with abstractable hydrogens were found to copolymerize via photoinitiation with a variety of electron donor monomers at a relatively rapid rate both in air and in nitrogen. In air, copolymerization rates of the dialkyl fumarates made from reaction of fumaric chloride with 1-methoxyisopropanol or 2-methoxy-1-ethanol were much faster than for monofunctional or difunctional acrylates when a photoinitiator was used to initiate polymerization. Mixtures involving dialkyl fumarates and N-vinylformamide (NVF) had polymerization exotherm rates faster than when N-vinylpyrrolidone and vinyl ethers were used as comonomers. Similar correlations with fumarate structure were observed when photoinitiator was present or absent, but faster rates were always obtained when a photoinitiator was present.