A mild and effective method for the direct acylcyanation of aryl alkenes with aroyl chlorides and trimethylsilyl cyanide (TMSCN) by merging photoredox and copper catalysis is described. This protocol uses commercially available starting materials to introduce acyl and cyano groups into a molecule simultaneously by direct bifunctionalization of alkenes in one step, which avoids the tedious pre-preparation of starting materials. The method is also applicable to aromatic and aliphatic sulfonyl chlorides to provide a series of β-sulfonyl nitriles. This procedure features good substrate tolerance and delivers 40 desired products with moderate to good yields.