A simple method for the synthesis of monoselenides and diselenides having 1,2,3-triazole ring is described herein. The three component reaction of ethynylstibanes, organic azides, and selenium powder is catalyzed by CuI (10 mol%) using 1,10-phenanthroline as the ligand (10 mol%) under aerobic conditions. Either selenides or diselenides can be synthesized by selecting the appropriate amount of selenium powder for otherwise identical reaction conditions. The obtained selenides and diselenides having a 1,2,3-triazole ring are all novel compounds. By using an antimony reagent, this one-pot reaction provides regioselective double Se-arylation under simple reaction conditions. Display omitted •The Cu-catalyzed three-component reaction of organoantimony, azides, and selenium is described.•The obtained selenides and diselenides having a 1,2,3-triazole ring are all novel compounds.•This reaction provides regioselective double Se-arylation under simple reaction conditions.