Polyaniline-metal composite incorporating binary transition metals was synthesized by in situ rapid mixing polymerization. The current article investigates the dielectric performance of polyaniline composite synthesized using ferric nitrate oxidant by a dopant-free template-free method and also the role of Cu2+ as an external redox additive in enhancing the dielectric performance of a PANI composite. The experimental results proved that the coordination of PANI nitrogen with binary transition metals (Fe & Cu) not only improved the electrical conductivity, but also augmented the dielectric performance. Also, morphological analysis substantiates the role of external Cu2+ additive in modifying the PANI surface to act as an efficient dielectric material.