Abstract: | An efficient method without using terminal arylacetylenes as substrates for the synthesis of bis(arylethynyl) selenides 1 (ArCC Se CC Ar) was described, and a series of compounds 1a−1m have been obtained by a one‐pot three‐step strategy from the corresponding bis(arylethanonyl) selenides. The mechanism was identified through trapping and characterization of a key intermediate 2a , and an elimination using it directly. The results from experiments indicated that the reaction procedure involves the formation of the enol phosphate and a subsequent base‐induced elimination. |