Because of its utility in network polymerization, dendrimer synthesis, and monomer development, the photoinitiated addition of thiols to alkynes has rapidly become an important tool for polymer scientists. Yet, because this chemistry has only recently been applied to cross-linked polymer development, understanding of the nature of how the yne structure affects the reactions and information on the relative reactivities of alkynes bearing various substituents is unavailable as is the relative addition rate of the thiol to the yne as compared to the vinyl sulfide. Herein, the photoinitiated addition of octanethiol to various alkynes is explored. The most rapid addition of thiols to alkynes is that to cyclooctyne, although the resulting vinyl sulfide does not permit subsequent thiol addition. Furthermore, in the absence of radical initiators and light, thiols add spontaneously to cyclooctynes, suggesting limitations to the orthogonality of the strain-promoted copper-less azide, alkyne cycloadditions. In order of decreasing reaction rates, the consecutive addition of two thiols occurs with the aliphatic 1-octyne > propargyl acetate > methyl propargyl ether > 2-octyne. Ethyl propiolate and methyl propargylamine exhibit very small reaction rates with thiols, and no consecutive addition is observed.