The electrochemical reduction of a series of aliphatic and aromatic bromides on glassy carbon, silver and copper electrodes has been investigated by cyclic voltammetry in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm]BF4). As in polar aprotic solvents, reductive cleavage of aromatic bromides occurs by a stepwise mechanism with the formation of a transient radical anion. In contrast, concerted electron transfer/bond rupture is the preferred reaction pathway for aliphatic bromides. Both Ag and Cu show remarkable electrocatalytic activities for the activation of the carbon-bromine bond, but the catalytic effect depends on reaction mechanism and molecular structure of RBr. Catalysis is high when reduction occurs by a concerted dissociative electron transfer pathway, which is the case of alkyl bromides. When instead a stepwise mechanism is preferred, i.e., the case of all aromatic bromides, catalysis strongly decreases with the ability of the molecule to delocalize the incoming negative charge. For example, the high positive shift of peak potential (> 0.7 V) observed for bromobenzene on Ag decreases to < 0.1 V for 4-bromobenzonitrile and < 0.02 V for 9-bromoanthracene. Overall, [BMIm]BF4 behaves like molecular solvents such as acetonitrile and dimethylformamide but, in general, both Ag and Cu are less active in the ionic liquid than in polar aprotic solvents.