A β-cyclodextrin-promoted [2+3] cycloaddition reaction between nitriles and sodium azide in the presence of ammonium chloride in DMF at 120 °C is reported, affording various 5-substituted 1H-tetrazoles in good to excellent yields in short reaction times. The presence of β-CD renders the formation of a precipitate-like gel in the reaction media when heated. No precipitation occurs in the absence of NaN₃ and NH₄Cl. The precipitation responses with other salts such as LiCl and NiCl₂ were weaker than with NH₄Cl. In the present paper the application of supramolecular aggregates is reported for the [2+3] cycloaddition reaction. β-Cyclodextrin can be recovered and reused without any significant loss of activity.