Herein we report on our studies on the sequential one‐pot combinations of amine‐catalyzed multicomponent reactions (MCRs). We have developed the copper‐free synthesis of functionalized bicyclic N‐aryl‐1,2,3‐triazole and N‐arylbenzotriazole products 4 and 5 from the simple unmodified starting materials through [3+2]‐cycloaddition ([3+2]‐CA) and oxidative aromatization reactions in one pot under amine catalysis. The sequential one‐pot reaction proceeds in good yields with high selectivity by using pyrrolidine as the catalyst from the simple unmodified substrates of enones, aryl azides, and 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ). Furthermore, we have demonstrated the medicinal applications of products 4 and 5 through simple organic reactions.