A practical and efficient approach for the synthesis of selenol and thiol esters is described via the reaction of acyl chlorides with diselenides or disulfides in the presence of Zn dust catalyzed by inexpensive CoCl2·6H2O This protocol tolerates a wide range of substrates, including aromatic and aliphatic acyl chlorides, with a variety of sensitive functional groups to afford the respective products in good yields. Furthermore, the method was also extended to use anhydrides as substrates. In addition, the obtained selenol esters could be readily transformed into vinyl selenide ketones by the selenocarbonylation of terminal alkynes catalyzed by a palladium/copper system.