Nitriles are widely existed in many bioactive compounds, and they can be easily transformed into other functional groups. Therefore, the synthesis of nitriles under cyanide-free conditions is of significant importance. Recent advances for the synthesis of nitriles through photoinduced C—C bond cleavage of cycloketone oximes classified by the type of C—X bond forming are summarized. Various compounds possessing nitriles can be efficiently accessed via this method.