The catalytic hydroarylation of nonactivated alkenes with aniline is a reaction of high interest, aiming at providing C-functionalized aniline derivatives that are important precursors for the fabrication of polyurethanes. However, this reaction remains a longstanding goal of catalysis, as it requires one to simultaneously address two important goals: (1) the very low reactivity of nonactivated alkenes and (2) control of the hydroarylation/hydroamination selectivity. As a result, the hydroarylation of aniline is mostly restricted to activated alkenes (i.e., featuring ring strain, conjugation, or activation with electron-donating or -withdrawing groups). Here we show that the combination of bismuth triflate and hexafluoroisopropanol (HFIP) leads to the formation of highly active catalytic species capable of promoting the hydroarylation of various nonactivated alkenes, such as 1-octene, 1-heptene, and 1-undecene, among others, with aniline with high selectivity (71-92%). Through a combined experimental and computational investigation, we propose a reaction pathway where HFIP stabilizes the rate-determining transition state through a H-bond interaction with the triflate anion, thus assisting the acid catalyst in the hydroarylation of nonactivated alkenes. From a practical point of view, this work opens a catalytic access to C-functionalized aniline derivatives from two cheap and abundant feedstocks in a 100% atom-economical fashion.