Polymer modification is a method of developing novel and/or tailor-made polymeric materials by altering the physical and/or chemical structure of existing polymers. To meet increasingly stringent and specific end-use requirements, polymers are normally modified by physically mixing it with another polymer with property not present in the former. This is known to be more economically feasible and readily achievable than homopolymers synthesized from new monomers. In this study, the feasibility of physically modifying a polymeric system composed of polyaniline (PANI) and polybenzoxazine (PBZ) is considered. The first polymer PANI, is known for its ease of synthesis, treatment, tuneable properties, low cost monomer, stability in both strongly alkaline and strongly acidic and good environmental stability in doped and neutral states. Moreover, interactions of PANI with metal surfaces lead to a beneficial anti-corrosion and capable of acting as antimicrobial/antifouling coating. The second polymer is PBZ has interesting features such as near-zero shrinkage upon polymerization, low water absorption, good dielectric properties, low surface free energy, and having the capability to exhibit thermal and flame retarding properties. With the advantages and limitations of each pure polymer in mind, physical modification by blending and nanofiller reinforcement is shown to reduce and eliminate the individual shortcomings of PANI and PBZ, and produce a multifunctional material with superior qualities. These superior qualities are demonstrated to be useful in high temperature, anti-corrosion, and antimicrobial applications.