An efficient and environment-friendly procedure for the synthesis of a new series of nitrogen bridge-head [1,2,4]triazolo[5,1-c][1,2,4]triazepine derivatives through one-pot three-component reaction of polyfunctional triazole with aromatic aldehydes and acetophenone derivatives using alcoholic sodium hydroxide solution. The same new products were prepared in classical route through reaction of triazole with the corresponding chalcones under the same conditions.