When α-benzylbenzoin (3a, α-benzyl-α-hydroxybenzyl phenyl ketone) was treated with potassium cyanide (1) in N, N-dimethylformamide at 80°C for 1 h, the carbon-carbon bond was cleaved, resulting in the formation of deoxybenzoin (4a, benzyl phenyl ketone) and benzaldehyde (2a). This carbon-carbon bond cleavage proceeds through a retro-benzoin condensation mechanism. This mothod of synthesizing ketones was applied to several α-substituted benzoins (3), and the corresponding ketones (4) were formed in good yields. Further, we found that the cyanide ion-donating ability of tetrabutylammonium cyanide (6, Bu₄NCN) is more effective than that of potassium cyanide (1, KCN). As expected from the chemical analogy between cyanide ion and azolium ylide, serveral azolium salts (7) can also be employed in the retro-benzoin condensation as catalysts.The benzoin derivatives 3 were synthesized in the following three ways; reaction of alkyl halide (9) with benzoin (5), Michael addition of benzoin (5) with acceptors (10), and Grignard reaction of benzils (8). Alkylation of the benzoins without isolation, followed by carbon-carbon bond cleavage, readily afforded the corresponding ketones (4).