Reaction of 5-arylethynyl-2-methyl-2H-tetrazoles (acetylene tetrazoles) with arenes under the action of Brønsted superacid CF ₃SO ₃H or acidic zeolite HUSY CBV-720 gives rise to E-/Z-5-(2,2-diarylethenyl)-2-methyl-2H-tetrazoles, as products of hydroarylation of acetylene bond, in yields up to 98% with predominant formation of E-isomers. Cationic intermediates of these reactions have been studied theoretically by DFT calculations. Addition of CF ₃SO ₃H to the triple bond of acetylene tetrazoles leads to the corresponding E-/Z-vinyl triflates in high yields. Hydration of triple bond in these tetrazoles in H ₂SO ₄ results in the formation of 5-(2-aryl-2-oxoethyl)-2-methyl-2H-tetrazoles. Tandem hydroarylation-ionic hydrogenation of acetylene tetrazoles in the systems acid(CF ₃SO ₃H or AlCl ₃)-arene-cyclohexane affords 5-(2,2-diarylethyl)-2-methyl-2H-tetrazoles.