Herein, a novel glycidyl carbamate functional epoxy resin (GCE) is synthesized by the additional reaction of the isocyanate group of tolylene diisocyanate (TDI) with the hydroxyl group of hydroxyl-terminated polybutadiene (HTPB) and glycidol. The successful synthesis of the GCE is confirmed by FT-IR and 1H NMR spectroscopy. Furthermore, a dual-curing adhesive system is developed using acrylic acid and trimethylolpropane triacrylate with varying GCE contents, and its adhesive performance is assessed by testing adhesive strength, pencil hardness, and surface energy. As a result, the dual-cure adhesive containing 0.2 mol of GCE demonstrates an impressive adhesive strength of 11.1 MPa, a pencil hardness of B, and surface energy comparable to that of standard polycarbonate film.