Poly(urethane-benzoxazine) films as novel polyurethane (PU)/phenolic resin composites were prepared by blending a benzoxazine monomer (Ba) and PU prepolymer that was synthesized from 2,4-tolylene diisocyanate (TDI) and polyethylene adipate polyol (MW ca. 1000) in 2 : 1 molar ratio. DSC of PU/Ba blend showed an exotherm with maximum at ca. 246 degreesC due to the ring-opening polymerization of Ba, giving phenolic OH functionalities that react with isocyanate groups in the PU prepolymer. The poly(urethane-benzoxazine) films obtained by thermal cure were transparent, with color ranging from yellow to pale wine with increase of Ba content. All the films have only one glass transition temperature (T-g) from viscoelastic measurements, indicating no phase separation in poly(urethane-benzoxazine) due to in situ polymerization. The T-g increased with the increase of Ba content. The films containing 10 and 15% of Ba have characteristics of an elastomer, with elongation at break at 244 and 182%, respectively. These elastic films exhibit good resilience with excellent reinstating behavior. The films containing more than 20% of Ba have characteristics of plastics. The poly(urethane-benzoxazine) films showed excellent resistance to the solvents such as tetrahydrofuran, N,N-dimethyl formamide, and N-methyl-2-pyrrolidinone that easily dissolve PUs. Thermal stability of PU was greatly enhanced even with the incorporation of a small amount of Ba.