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Herein, we report on the rhodium‐catalyzed reaction of triazoles with acyl selenides. Under thermal reaction conditions and in the presence of a rhodium catalyst, a rapid 1,3‐difunctionalization reaction occurs to provide valuable α‐seleno enamides with high stereoselectivity and broad functional group tolerance, which was demonstrated in 35 examples with up to 95% yield. Computational calculations suggest a reaction pathway that gives a direct access to the 1,3‐difunctionalization without intermittent formation of ylide intermediates. [ABSTRACT FROM AUTHOR]