Polyurethane (PU) prepared by blending rosin base and CO2-polyol already has good mechanical properties and hydrophobic effect and has powerful benefits in acid and alkali resistance and salt resistance. In this study, mussel bionic rosin-based benzoxazine (BZ) was synthesized using dehydroabietylamine, catechol, and paraformaldehyde. Mixing BZ into PU can endow the resulting PU/BZ with special effects such as zero curing shrinkage, excellent mechanical behavior, and flame retardancy through a 3D interpenetrating network system. From the results, the modulus of rupture (MOR) and modulus of elasticity (MOE) of PU wood coatings are 97.04 and 2601.97 MPa, respectively; in contrast, the PU/BZ wood coatings exhibited higher values of MOR and MOE of 110.87 and 2738.11 MPa. PU/BZ wood coatings show higher flexural strength and elastic modulus. They are also stronger than PU coatings in terms of acid/alkali and aging resistance. At the same time, the coating is endowed with flame retardant properties, and the LOI is 30.2 due to the presence of BZ. Thus, PU/BZ can be a versatile and practical wood coating. The interpenetrating network system of PU/BZ has an innovative impact on the preparation of wood coatings.