Herein reported is a nickel-catalyzed reductive aryl thiocarbonylation of alkene via thioester group transfer strategy by using simple and readily available thioesters. In contrast to traditional activation of weaker C(acyl)-S bond, the C(acyl)-C bond of thioester was selectively cleaved to enable this reaction under mild conditions. Furthermore, this approach features operational simplicity and broad substrate scope, providing a complementary and practical route for thioester synthesis without requiring toxic thiol or CO gas.