This work examines the electrochemical behavior of "iodized silver derivatives," pure or adsorbed on solid industrial wastes, in order to devise an electrochemical process for metal recovery from matrices containing these species. Voltammetric, coulometric and adsorption measurements were used to determine the reduction mechanism of silver derivatives at the electrode and to propose a reaction rate law depending on operating conditions.Mass balances and electrical balances of electrolyses of aqueous suspensions of solid wastes led to a better understanding and to the optimization of the overall electrochemical process of silver recovery. Comparison of experimental and theoretical results indicates the feasibility of the process proposed. (C) 2003 Elsevier Ltd. All rights reserved.