Polymers of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate were prepared by photoinitiated polymerizations in the presence of 2,2-dimethoxy-2-phenyl-acetophenone at 27°C. The reactions led to highly crosslinked polymeric networks. The volume shrinkage observed during polymerization was a function of the number of ethylene glycol units in the dimethacrylate monomer. The kinetic rate constants of polymerization, as determined from the photopolymerization characteristics using a dilatometric technique, were again dependent on the number of ethylene glycol units in the monomer. The importance of these results on the crosslinked structure of the prepared networks is discussed.