In this work we report the unique electrocatalytic role of benzoic acid protected silver nanoclusters (Ag(n), mean core diameter 2.5 nm) in the Wolff rearrangement (Scheme 1) of alpha-diazoketones. More specifically, the presence of a Ag(n) (0)/Ag(n) (+) redox couple facilitates a nonclassical electron-transfer process, involving chemical reaction(s) interposed between two electron-transfer steps occurring in opposite directions. Consequently, the net electron transfer between the electron mediator (Ag(n)) and alpha-diazoketone is zero. In-situ UV-visible studies using pyridine as a nucleophilic probe indicate the participation of alpha-ketocarbene/ketene as important reaction intermediates. Controlled potential coulometry of alpha-diazoketones using Ag(n) as the anode results in the formation of Wolff rearranged carboxylic acids in excellent yield, without sacrificing the electrocatalyst.