In summary, we have developed an operationally simple and scalable methodology from commercially available starting materials for the formation of trisubstituted pyridines through the triphenylamine and benzoic acid promoted electrochemically induced [2+2+2] annulation of aromatic alkynes with nitriles. Especially, we have identified two classes of alkynes (EoAs and EnoAs) depending on their ability to undergo electrochemical oxidation and have successfully engaged them with nitriles in an intermolecular three-component cross-annulation, being the first of its kind. Additionally, the effectiveness of the developed protocol has been demonstrated by scalability in batch and continuous-flow processes. The synthetic diversification to access π-extended aromatics emphasizes the utility of this method. A plausible mechanism has been proposed, supported by a series of mechanistic studies, radical quenching experiments, CV, EPR, NMR, and computational studies. The here developed electrochemical strategy is complementary to the well-established and metal-mediated [2+2+2]-cycloaddition between alkynes and nitriles but stands out in its ability to allow cross-annulations with two alkynes with high chemo-and regioselectivity.