The installation of selenium groups has become an essential step across a number of industries such as agrochemicals, drug discovery, and materials. However, direct C(sp3)-H selenation, which is most atom economical, remains a formidable challenge, and only a few examples have been reported to date. In this article, we introduce the transition metal-free C(sp3)-H selenation with the easily available β-ketosulfones and diselenides as the material source. This benign protocol permits access to a broad spectrum of α-aryl(alkyl) seleno-β-ketosulfones in high yields with outstanding functional group compatibility. Distinct advantages of this protocol over all previous methods encompass the utilization of base and air as an oxidant, room temperature, and enhanced green chemistry matrices.