Polypyrrole (ppy) coatings doped with p-toluene sulfonate sodium on stainless steel mesh (SSM) have been electrosynthesized in aqueous solution. The removal of Ag+ ions from acidic solutions was investigated through spontaneous reduction (SR) and electrochemical reduction (ER) procedures using reduced composite ppy-SSM. Higher removal efficiencies and current efficiencies were obtained by ER process for ppy-SSM rather than SR process for ppy-SSM and ER process for SSM under comparable conditions. Due to its high efficiency and simplicity, ER was supposed to be an alternative advantageous method for the recovery of low-level silver concentration in industrial wastewater. Cyclic voltammetry was carried out to characterize the electrochemical behavior of ppy-SSM in acid solutions containing Ag+. Metallic silver deposited on ppy-SSM has been evidenced by scanning electron microscopy (SEM) analysis.