4-Nitro-1,2,3-triazoles are crucial precursors for high energy materials, and their practical synthesis is a long-standing problem. Herein, we communicate a mechanochemical route for the selective synthesis of 4-nitro-1,2,3-triazoles via organocatalyzed oxidative [3 + 2] cycloaddition between β-nitrostyrenes and organic azides. Our conditions avoid divergent pathways and permit the retention of the valuable NO2 group on the product. Nontoxic catalyst, catalyst recyclability, no rigorous solvent-extraction, no toxic byproducts, atmospheric oxygen, and gram-scale synthesis are some of the salient features.