We describe an organophotoredox-catalyzed sp3 C-S coupling of N-sulfinylamines with bench-stable alkyltrifluoroborates as a latent nucleophilic counterpart en route to alkylsulfinamides in high efficiency. In contrast to the two-electron reactivity of traditional organometallic reagents, this catalytic method reports the single-electron process of an organometallic reagent with N-sulfinylamines in C-S coupling. This mild and scalable protocol offers operational simplicity and exceptional functional group compatibility, including ketone, ester, amide, nitrile, and halides, that is vulnerable to organolithium or Grignard reagents. Additionally, the sulfinamides are conveniently converted to a variety of important S(VI) compounds, like sulfonamides, sulfonimidamides, and sulfonimidates, among others.