The silver reduction process was studied in a new, low cyanide concentration solution in which the predominant species is the ion and the pH is fixed by the presence of potassium pyrophosphate. The electrochemical reduction of silver occurs via an adsorbed electroactive species assumed to be . The silver reduction appears to be a quasi‐reversible process at 20°C, and its kinetic parameters are presented as well as the effect of temperature in a 10 to 60°C range; silver reduction is fast when the temperature is high, and the activation energy was evaluated. Linear sweep voltammetry and the use of an electrochemical quartz crystal microbalance prove the existence of the adsorbed electroactive species and additional evidence was found by chronopotentiometry.