The electrochemical properties of 2,5-dimercapto-1,3,4-thiadiazole (DMcT)–polyaniline (PAn) composite films containing Ag nanoparticles (Ag-NPs; Ø 17nm) were investigated. Adding the nanoparticles to DMcT–PAn composites, charge–discharge performance of the composite was enhanced due to electrocatalytic activation of DMcT by the nanoparticles. Optimum content of the Ag-NPs was 5wt.%. The observed current enhancement was ascribed to the improve efficiency of DMcT utilization in the composites due to electrocatalytic activation of the DMcT redox reactions in the presence of Ag-NPs.