Sulfoxides are ubiquitous in both naturally and synthetically bioactive molecules. We report herein a redox-neutral and mild approach for radical sulfinylation of redox-active esters via dual photoredox and copper catalysis, furnishing a series of functionalized sulfoxides. The reaction could accommodate a range of tertiary, secondary, and primary carboxylic acids, as well as exhibit wide functional group compatibility. The chemistry features a high degree of practicality, is scalable, and allows late-stage modification of bioactive pharmaceuticals.