A versatile approach for the alkynylation of a variety of aliphatic hydrogen donors, including alkanes, is reported. We used tetrabutylammonium decatungstate as photocatalyst to generate organoradicals from C-H/Si-H bonds via hydrogen atom transfer. The latter intermediates underwent SOMOphilic alkynylation by methanesulfonyl alkynes to afford internal alkynes upon loss of a sulfonyl radical. The effect of different radicofugal groups on the reaction outcome was evaluated and rationalized via a combined experimental and computational approach.