Fundamental study has been performed for synthesis of silver cyanide through electrochemical leaching process. Silver was used as anode, stainless steel (STS 316) as cathode and proton exchange membrane (Nafion 117) as a separator between electrodes. Concentration of silver leached was analyzed by ICP-OES. Surface and cross section were analyzed by SEM and EDS. After 20 min, 19.4% leaching of silver at standard condition (voltage alone, no stirring and air-bubbling), 70 % in stirring, 80.9% in air bubbling were measured. Electric current efficiency in air-bubbling was 102%, which means chemical dissolution as well as electric leaching was done during reaction. After reaction, silver ions were not detected in cathode electrolyte. Dissolved silver ion might directly react with cyanide ion to make negative complex silver cyanide ion that can not penetrate proton exchange membrane.