Thioesters　and　related　thiols　are　critically　important　to　biological　systems　and　also　widely　employed　in　the　synthesis　of　pharmaceutically　important　molecules　and　polymeric　materials.　However,　known　synthetic　methods　often　suffer　from　the　disadvantage　of　being　specific　only　to　certain　substrates.　Herein,　we　describe　a　facile　decarboxylative　thioesterification　of　alkyl　acid　derived　redox-active　esters　by　merging　photoredox　catalysis　and　copper　catalysis.　This　reaction　is　applicable　to　a　wide　range　of　carboxylic　acids,　as　well　as　natural　products　and　drugs,　allowing　for　the　synthesis　of　various　thioesters　with　diverse　structures,　including　tertiary　ones　that　are　not　accessible　via　traditional　nucleophilic　substitution　from　tertiary　halides.　Moreover,　product　utilization　is　demonstrated　with　a　direct　transformation　of　thioesters　to　sulfonyl　fluorides.