The present work deals with the electrochemical synthesis of poly-4-methyl-3-mercapto-1,2,4-triazole (p-MMTA)/TiO2 composite on metallic copper to evaluate its corrosion protection. The composite was characterized by FT-IR, cyclic voltammetry, X-ray diffraction and energy dispersive X-ray analysis. The distribution of inorganic particles in the polymeric matrix was evidenced from the scanning electron microscopic studies. The corrosion performance of composite coating was evaluated by electrochemical impedance spectroscopy and Tafel polarization measurements in 3.5 % NaCl medium. The p-MMTA/TiO2 composite showed an excellent corrosion protection ability, which was evidenced from the results of electrochemical measurements. The enhanced ability could be due to the barrier effect of composite coatings against corrosive species and also due to the synergistic effect between organic polymer and inorganic particles.