An　efficient　method　for　the　copper-catalyzed　selective　C−H　difluoroalkylation　of　coumarins　and　with　low　cost　and　readily　available　ethyl　bromodifluoroacetate　and　N-phenyl　bromodifluoroacetamide　has　been　reported.　This　reaction　exhibits　good　functional　group　tolerance　with　respect　to　coumarins　and　difluoroalkylation　reagents,　and　several　redox-sensitive　substrates　have　been　successfully　C−H　difluoroalkylated　in　good　to　high　yield.　This　design　could　further　expand　the　scope　to　other　heteroarenes,　including　furan,　benzofuran,　pyrrole,　pyridinone,　chromenone,　indole,　and　quinolinone.　A　mechanism　involving　copper-catalyzed　in-situ　generation　of　fluoroalkyl　radical　is　proposed.　©　2020　Wiley-VCH　GmbH