Microwave technology has emerged as a great tool for the efficient synthesis of organic compounds and provides opportunities for the chemists to achieve adequate chemical transformations, which were amenable to...

The application of microwave technique in chemical laboratory rooted back in 1986 and found advantageous over conventional approaches. On the other side, poly‐aza‐heterocycles are influencing organic frameworks with a fascinating chemistry and well explored by employing microwave‐assisted organic reactions. In the present review, we have thoroughly updated rousing literatures of microwave‐assisted synthesis and reactions of various poly‐aza‐heterocycles viz., triazole, tetrazole, triazine, and tetrazine from the past decade (2010–2020). The expedient chemistry and enabling role of microwave heating for adequate chemical transformations of such heterocycles, which were more challenging using classical approaches, are appropriately elucidated. This review also highlights the potential applications of these heterocyclic scaffolds and their derivatives in different scientific domains. Remarkably, such chemical architects possess wide applications as crucial building blocks in synthesis of biologically relevant compounds, agrochemicals, and compounds of interest in material science.