The conversion of aldose into two one‐carbon‐higher epimeric homologs, which involves a nucleophilic addition of cyanide to the terminal carbonyl group of an aldose, hydrolysis of cyanohydrin, and reduction of the resulting lactone is generally known as the Kiliani–Fischer cyanohydrin synthesis. The study finds that alkaline conditions are required to maintain high effective concentration of cyanide for the performance of the reaction. This reaction is useful for the preparation of higher‐order aldoses and isotope‐labeled carbohydrates.