A series of pH-sensitive and thermosensitive polymer networks were first obtained by copolymerization of telechelic poly(1,3-dioxolane) (PDXL) with acrylic acid (AA), acrylamide (AM), and N-isopropylacrylamide (NIPAM), respectively. The copolymerization of PDXL diacrylate (PDXLDA) with AA, AM, or NIPAM is expected to lead to polymer networks in which homopolymeric segments of the monomer are connected by polyacetal segments. As a combination of these two parts, these polymer networks can have some interesting physical properties. For example, the copolymer networks of poly(AA-b-DXL) showed pH sensitivity, and both the copolymer networks of poly(AM-b-DXL) and poly(NIPAM-b-DXL) showed temperature sensitivity. Moreover, because of the low ceiling temperature of polyDXL, the networks containing polyacetal segments (PDXL) can degrade by treatment with a trace of appropriate cationic initiator. The polymer networks prepared were characterized by Fourier transform infrared, differential scanning calorimetry, and swelling data.