In seeking to broaden the lexicon of photocatalysis and considering the importance of sulfones as essential pharmaceuticals, herein one-pot visible-light-induced tertiary C(sp3)-H sulfonylation is explored for the first time using indoline-2,3-diones, 4-hydroxy proline, and sulfinic acids as model substrates in the presence of iodine and Na2-Eosin Y as a photocatalyst. In addition, this transformation unlocks a new strategy in the context of the late-stage tertiary C(sp3)-H sulfonylation of Monastrol, a selective Eg5 inhibitor, and its analogue.