Processing conditions during free radical polymerization strongly affect the polymer network evolution. This work focuses on how the solvent quality during solution polymerization alters the mechanical and structural properties of the resulting polymer hydrogel network in methacrylate copolymerizations. Two copolymer systems were analyzed: 2/98 diethylene glycol dimethacrylate/methoxyethyl methacrylate and 2/98 diethylene glycol dimethacrylate/octyl methacrylate. Copolymerizations were performed in varying amounts of either hexanol or ethylene glycol diacetate. The equilibrium swelling of bulk DEGDMA was also measured to ascertain how the cross-linking agent interacts with the solvent. To compare the solvent quality of the two solvents, the equilibrium swelling of the copolymer samples was measured in each solvent. The results of dynamic mechanical analysis illustrate that changes in solvent concentration and solvent quality affect the extent of primary cyclization during the polymerization. The results further demonstrate how solvent-polymer interactions influence the network structure in copolymerizations where the monovinyl monomer and cross-linking agents may each interact differently with the solvent. Experimental results are compared to theories for how the structural evolution, especially the cross-link density, changes with solvent amount and quality.