Organic azides are synthetically and commercially useful intermediates with a wide variety of applications. In this work, azidative aromatization of quinone methides under transition metal and acid‐free conditions can avoid the forming of highly toxic and explosive hydrazoic acid and azide salts. The use of cesium carbonate as a catalyst and water as an effective additive, elimination of a transition metal catalyst, reaction solvent, and column chromatography separation led to an overall greener approach to access valuable benzyl azides in quantitative yields. Because the procedure can be used to prepare a serious of benzyl azides without contamination by any harmful transition metal residues, this new method has great potential in pharmaceutical synthesis and chemical biology studies.