The rhodium-catalyzed reductive cleavage of carbon-cyano bonds is developed using hydrosilane as a mild reducing agent. A wide range of nitrites, including aryl, benzyl, and B-hydrogen containing alkyl cyanides are applicable to this decyanation reaction. The method can also be applied to organic synthesis; the use of benzyl cyanide as a benzyl anion equivalent and the use of a cyano group as a removable ortho-directing group are demonstrated.