A novel, mild approach featuring simplified operation has been developed for the direct synthesis of complex N-aryl tertiary amines via a three-component reaction, utilizing an electron donor-acceptor (EDA) complex strategy. In contrast to previous studies, which have primarily focused on two-component reaction systems for the functionalization of N-aryl tertiary amines, our method enables the functionalization of a diverse range of nitrogen-containing heterocyclic compounds and N,N-dialkylanilines under the established reaction conditions.