A highly selective nickel-catalyzed C–H trifluoroethylation of heteroarenes was developed with the assistance of a monodentate directing group. This protocol provides efficient access to various trifluoroethyl-substituted heteroarenes, including indoles, pyrroles, furans, and thiophenes, with commercially available CF₃CH₂I as an alkylation reagent. This robust catalytic procedure is scalable and tolerates a broad range of functional groups. Moreover, multifluoroalkylation of indoles is also viable.