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As a privileged motif, tetrazoles can be widely found in pharmaceuticals and materials science. Herein, a five-component reaction of cycloketone oxime esters, alkynes, DABCO·(SO2)2, and two molecules of trimethylsilyl azide under iron catalysis is developed, giving rise to a range of cyano-containing sulfonylated tetrazoles in moderate to good yields. This multicomponent reaction exhibits excellent selectivity and enables the formation of multiple new chemical bonds in one pot. A possible mechanism involving azidosulfonylation of alkynes