Abstract Herein, we developed a metal‐free, photosensitized strategy for difunctionalization of olefin feedstocks to access β‐amino sulphone architectures, enabled by a tailor‐made, readily accessible sulfonylamide bifunctional reagent. This protocol could accommodate a wide range of alkenes and a variety of sulfonylamides, with high yields and excellent regioselectivity. Given remarkably mild reaction conditions, readily accessible starting materials, excellent functional group tolerance, and well‐defined regioselectivity, this approach would enable an efficient platform for the assembly of densely functionalized molecular scaffolds.