Thiol-yne reactions typically employ thiols and terminal alkynes as the reaction partners. The thiol-yne reaction of alkynyl sulfides and thiols is possible when employing a nonmetal photocatalyst eosin Y, green LED irradiation, under an air atmosphere. Alkynyl sulfides were transformed in good overall yields (58-90% total yields, 11 examples) favoring the cis isomer. No addition to the α-position of the alkynyl sulfide is observed, and regioselectivity is believed to be controlled through the stabilization of radical intermediates by the adjacent sulfur atom. Furthermore, control experiments with "all-carbon" internal alkynes demonstrate that alkynyl sulfides possess improved reactivity and regioselectivity profiles during thiol-yne processes.