Tri-functional methacrylate (MA3) having thermally degradable tertiary ester linkages was synthesized by a convergent approach. When the MA3 film containing a thermal initiator and a photoacid generator was heated under nitrogen atmosphere, it became insoluble. The thermally cured MA3 became soluble after irradiated and followed by baking at 120°C. Acid catalyzed decomposition of the tertiary ester linkages of the MA3 moiety occurred at lower temperatures than noncatalyzed one. A mechanism for the photo-or thermal curing and photoassistedthermal degradation was studied by FT-IR, 1 H NMR, TGA, MS, and SEC analyses.