New type of amphiphilic pH-sensitive polyurethane networks, derived from the mixture of polyethylene glycol-modified urethane acrylates (PMUA) and urethane acrylate anionomer (UAA), were prepared and their swelling behaviors were evaluated. Three kinds of polymerization methods were employed in the synthesis of polyurethane networks. Polyurethane networks prepared by a process similar to that of soap-free emulsion polymerization (UAHG) showed the highest swelling ratio and pH-sensitivity Additionally, four kinds of UAHG gels were prepared at different composition of UAA. As the composition ratio of UAA to PMUA increased, swelling of UAHG gels in alkali pH buffer solution and their pH-sensitivity greatly increased. Additionally, swelling of UAHG gels changed reversibly with the change of pH.