A copper‐catalyzed efficient synthesis of alkynyl thioamides starting from tetraalkyl thiuram compounds (TMTM: tetramethyl thiuram monosulfide, TIBTM: tetraisobutyl thiuram monosulfide) and alkynes was reported. Thus, tetraalkyl thiurams reacted with alkynes smoothly, giving a variety of alkynyl thioamides promoted by CuI/Cs2CO3 system. This protocol features easy operation, inexpensive starting materials and good yields, illustrating its potential synthetic value for the synthesis of thioamides and their derivatives.