Polymer networks that can serve as model systems for dental applications were prepared by photopolymerizations of 1,1,1-trimethylolpropane triacrylate, 1,1,1-trimethylolpropane trimethacrylate, 1,1,1-trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Photomer 2028 and Photomer 3015. The UV polymerizations were initiated by 2,2-dimethoxy-2-phenyl-acetophenone. Volume shrinkage was followed over the course of polymerization using a dilatometric technique. Incident light intensities ranged from 1 mW cm-2 to 20 mW cm-2. The effects of monomer structure on % volume shrinkage, including pendant group size, molecular weight between reactive double bonds, and acrylate versus methacrylate monomers were investigated. In addition, the effect of incident light intensity on % volume shrinkage was studied. Typical volume shrinkage varied from 3.5% to 13.5%. The volume shrinkage decreased with increasing monomer rank and increased pendant group size; the shrinkage for methacrylates was less than that for acrylates. Increased incident light intensity resulted in increased shrinkage rate, but not in statistically significant increases of the volume shrinkage. Conversion was calculated from shrinkage data and compared to data from monomer extraction experiments. Results indicate that although double bond conversion is low, conversion of monomer units is significantly higher.