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In this study, we reported the ammonium metavanadate (NH4VO3) as an efficient, cost-effective, and mild catalyst for the synthesis of substituted pyridines via a one-pot pseudo four-component reaction. Furthermore, we investigated Hantzsch 1,4-dihydropyridines (1,4-DHPs) synthesis and oxidation of 1,4-DHPs to their corresponding pyridines. The present approach offers a rapid methodology for accessing various pyridines with broad functional group tolerance and good yields using NH4VO3 catalyst as a green catalyst.