A novel procedure for the preparation of various 5‐aminotetrazoles derivatives was achieved using trichloroisocyanuric acid as a desulfurizing agent of thioureas and trimethylsilyl azide in ethyl acetate at room temperature. This methodology provided substituted 5‐aminotetrazoles through a more sustainable reaction using an affordable, safe, stable, and easily handled N‐halo reagent, a safer azide source, and an environmentally friendly solvent.