A new electrochemical procedure for the electrocatalytic carboxylation of aromatic ketones with carbon dioxide in ionic liquid, 1-butyl-3-methylimidazolium tetrafluoborate (BMIMBF4), to α-hydroxycarboxylic acid methyl ester was investigated for the first time. The electrochemical behavior of acetophenone in BMIMBF4 was studied by cyclic voltammetry with a reduction peak at −1.9V (vs. Ag). The electrolyses experiments were carried out in an undivided cell under mild conditions without any toxic solvents, catalysts and supporting electrolytes, followed by addition of an alkylating agent, affording the α-hydroxycarboxylic acid methyl ester in a moderate yield (62%). The results showed that the yields were strongly affected by various factors: temperature, current density, charge passed, electrode material and substrate concentration. Moreover, the ionic liquid was successfully recycled for this reaction.