Polybenzoxazine (PBz)-based conducting materials have gained significant attention due to their unique combination of thermal stability, mechanical strength, and electrical conductivity. These polymers integrate the inherent advantages of polybenzoxazines-such as low water absorption, high glass transition temperature, and excellent chemical resistance-with the electrical properties of conducting polymers like polyaniline, polypyrrole, and polythiophene. The incorporation of conductive elements in polybenzoxazine networks can be achieved through blending, in situ polymerization, or hybridization with nanostructures such as graphene, carbon nanotubes, or metallic nanoparticles. These modifications enhance their charge transport properties, making them suitable for applications in flexible electronics, energy storage devices, sensors, and electromagnetic shielding materials. Furthermore, studies highlight that polybenzoxazine matrices can improve the processability and environmental stability of conventional conducting polymers while maintaining high conductivity. The structure-property relationships of polybenzoxazine-based composites demonstrate that tailoring monomer composition and polymerization conditions can significantly influence their conductivity, thermal stability, and mechanical properties. This review summarizes recent advancements in PBz composites, focusing on their synthesis, structural modifications, conductivity mechanisms, and potential applications in advanced energy storage systems.