The reductive cleavage of a series of organic halides, including both aromatic and aliphatic compounds, has been investigated in acetonitrile at glassy carbon (GC) and silver electrodes. Ag exhibits extraordinary electrocatalytic activities for the reduction of most of the investigated halides. During the reductive cleavage of a carbon–halogen bond, electron transfer (ET) and bond breaking may occur either in a single step or in two distinct steps. The compounds examined in this study are representative of both dissociative electron transfer (DET)mechanisms. In general a link between the DET mechanism and electrocatalysis at Ag is observed for the whole set of data.There is no catalysis at all when the ET involves a substituent that gives a stable radical anion. Furthermore, there is no catalysis for all aromatic chlorides. Instead, a remarkable electrocatalysis is observed for all compounds undergoing a concerted DET mechanism, regardless of the nature of the halogen atom.