A photochemical cross-coupling protocol towards bi(hetero)aryls has been developed. The coupling reactions were mediated by dicyanopyrazine photoredox catalyst, while a photoinduced disproportionation process has been identified as an accompanying mechanism, especially for pyrrole derivatives. The developed method allows the cross-coupling of five-membered rings such as pyrrole, imidazole, thiazole and oxazole as well as various diazines (pyridine and pyrimidine) and benzene derivatives. A plausible mechanism of the reaction has also been disclosed. The practical application and relevance of the developed method were demonstrated by constructing an atorvastatin core or by the gradual functionalization of benzo[c][1,2,5]thiadiazole. In total, twenty-one bi(hetero)aryls were prepared in yields ranging from 19 to 95%.