In this paper we wish to report a highly selective and benign method for the double C–H/C–H coupling of azaaromatics with indoles or pyrrole in the presence of air oxygen/TiO₂, as an effective photocatalytic oxidative system. It has been shown that this versatile approach can be applied for direct C–H functionalisation of a variety of azaaromatic systems, such as mono-, di- and triazines, substituted and unsubstituted azines and their benzo-annelated analogues.