Herein, we report a AgF-mediated regio- and stereoselective acetoxyselenylation of terminal/internal alkynes from iodobenzene dicarboxylate [PhI(OCOR)2] and diorganyl diselenides via multiple-site functionalization to afford β-selenyl enol esters in good yields. Alkynes derived from bioactive molecules, such as l(-)-borneol, l-menthol, and acyne oxalate, are also suitable for this transformation and afford the expected compounds.