A reaction involving formal alkadiene insertion into a C-CN bond taking place via a catalytic photo-NOCAS mechanism was developed. The process involves photoirradiation of an acetonitrile solution containing 2,5-dimethy1-2,4-hexadiene (1), p-dicyanobenzene (p-DCB), phenanthrene (Phen), and a catalytic amount (20 mol %) of tetra-n-butylammonium cyanide. The reaction proceeds in the absence of noble metals and under mild conditions (ambient temperature without bases). This is the first example of a photo-NOCAS reaction in which a catalytic amount of nucleophilic species is employed to promote the process.