Recently, low-cost and high efficiency recovery technology has been applied to the purification of silver-containing waste liquid, which has become one of the hotpots in the field of secondary resource recovery. This research is aimed at Ag replacement from the silver-containing waste liquid produced in the electrolytic refining of silver by copper replacement method, using metal copper as the anode substrate, and the noble metal silver ions in the waste liquid to form a redox system. No chemical reagents is added to the replacement reaction. The results show that the decrease of the solution pH value is conducive to the replacement reaction, extending the reaction time can make the replacement reaction complete, increasing the temperature can accelerate the replacement reaction rate. On the basis of optimum condition, recovery rate of silver can reach 99.7% and silver purity reaches ≥98.5%.This method can be successfully applied to the recovery of silver from the waste liquid.