Transition metal- and photosensitizer-free C(sp3)-H (sulfonyl)amidation reactions have been realized by employing Selectfluor® as a versatile reagent, functioning as a photoactive component, a HAT precursor and an oxidant. Various toluene derivatives, cycloalkanes, natural products and bioactive molecules can be converted into N-containing products under mild conditions in good yield and with high chemo- and site-selectivity.