A new electrochemical procedure for the electrocatalytic dimerisation of benzoyl chloride in ionic liquid, 1‐butyl‐3‐methylimidazoliumtetrafluoborate, to benzil was investigated for the first time. The electrochemical behavior of benzoyl chlorides in BMIMBF4 was studied by cyclic voltammetry with a reduction peak at −1.2 V (vs Ag). The electrolysis experiments were carried out in an undivided cell under mild conditions without any toxic solvents, catalysts and supporting electrolytes, creating benzil at a moderate yield (51%). The results showed that the yields were strongly affected by various factors: temperature, working potential, electrode material. Moreover, the ionic liquid was successfully recycled for this reaction. Copyright © 2011 John Wiley & Sons, Ltd.