The [2þ3] cycloaddition between various nitriles and crosslinked poly(4-vinylpyridine) supported azide ion proceeds smoothly in the presence of ammonium bromide or ammonium chloride in N,N-dimethyl formamide, to give the corresponding 5-substituted-1H-tetrazoles in good to high yields. Conventional heating was used to promote reaction. It was found that using nitriles with electron-withdrawing groups result in bout higher yields and lower reaction times. The present procedure offers advantages, such as shorter reaction time, and simple workup.