The formation of silver-palladium electrodes is described. It mainly corresponds to the palladization of silver by means of treatment with palladium salts (nitrate and sulphate) in acidic media. Other ways may exist such as the modification of solid conductors like carbons by deposition of a silver-palladium alloy. By using those electrodes in polar aprotic solvents, the one-electron cleavage of carbon-halogen bonds of most alkyl iodides and bromides may yield free alkyl radicals. Coupling and cross-coupling reactions can easily be carried out at such electrodes. The present review aims at discussing the electro-catalytic process as well as providing an update on the state of the art on this new mode of scission regarding carbon-heteroatom bonds. (C) 2010 Elsevier Ltd. All rights reserved.