Amphiphilic urethane acrylate anionomer (UAA) chains exhibited very different solution properties in various solvents, such as water, dioxane, and dimethyl sulfoxide (DMSO). UAA chains showed a polyelectrolyte effect in a highly polar solvent, DMSO, but gave constant viscosity at various concentrations in aqueous solution, because of the microstructural difference of the UAA chain formed in solvents. In polar solvents (water and DMSO), the swelling of UAA networks prepared with water and dioxane strongly depended on the properties of the hydrophilic domains. In low and nonpolar solvents (dioxane and methylene chloride), the swelling of UAA networks was only dependent on the property of the hydrophobic segments. In the polar solvent medium, UAAG networks prepared with water exhibited greater swelling than UADG networks prepared with dioxane. Concerning swelling in a nonpolar solvent, however, UADG networks showed greater swelling than UAAG networks. This is because of the microstructural difference between these networks, which was confirmed by the mechanical, property measurement. UAAG networks, having highly microphase-separated structures, had higher modulus and transition temperatures than the UADG networks, because of the microstructural difference between UADG and UAAG networks. Both the UAAG and UADG networks take up two immiscible solvents simultaneously within their hydrophobic and hydrophilic domains. Equilibrium swelling ratio of these networks in two immiscible solvents strongly depends on their hydrophilic/hydrophobic balance that is controlled by the type of solvent used in the network synthesis.