Montmorillonite KSF has been used as an effective and non-toxic heterogeneous catalyst for one-pot synthesis of 5-substituted 1H-tetrazoles via [3+2] cycloaddition of sodium azide with a wide variety of nitriles. The reaction afforded high yields of the desired products in a short reaction time under mild reaction conditions. The catalyst can be recovered by simple filtration and reused for more consecutive trials without a significant decrease in activity. To avoid using toxic catalyst and catalyst recycling make this synthesis a truly green procedure.