Abstract Azaphosphatranes were found to act as efficient organocatalysts in the presence of water for the cyanation of differently substituted imines. A relatively safer source of cyanide, trimethylsilyl cyanide (TMSCN), was used, and excellent yields could be obtained with only 0.05 mol % of catalyst. The influence of acidity of azaphosphatranes on catalytic activity as well as the role of azaphosphatranes in the mechanism of the reaction were also investigated.