In this study, the electrodeposition-redox replacement (EDRR) method was studied for the recovery of minor concentrations of silver from dilute solutions. The parameter optimization was carried out with synthetic solutions similar to silver oxide button battery recycling effluents, consisting of sulfuric acid and concentrated base metal (10 g·L⁻¹ H₂SO₄, 60 g/L Zn²⁺) with a minor amount of silver (100 ppm) and a varying amount of Fe³⁺ ions. Results of these experiments were analyzed both electrochemically and by use of SEM-EDS. The role of dissolved Fe³⁺ ions was studied by varying the concentration from 0 to 1000 ppm and the results showed that although the presence of Fe ions decreased silver recovery efficiency, final product purity was found to increase slightly. The EDRR process was also found to be more effective for Ag recovery and has less energy consumption when Fe³⁺ concentrations are relatively low (≤ 100 ppm) when compared with conventional direct current electrowinning. In the final stage, silver was successfully recovered via EDRR, using the optimized conditions, from a real pregnant leaching solution (PLS) obtained from the leaching of silver oxide batteries.