Hydroarylation of alkenes is one of the most straightforward and atom-economical strategy for the construction of multi-aryl-substituted alkanes, but systematic studies have been limited to transition metal catalysis. Here we report a hexafluoroisopropanol (HFIP)-promoted hydroarylation of alkenes with indoles without the presence of transition metal catalysts or any additive. HFIP was the only reagent used in this work, and could be easily removed via evaporation, and recovered via distillation in industry settings. This reaction was shown to provide an efficient, clean and operationally simple procedure with a remarkable substrate scope and versatile transformations, delivering a variety of multi-aryl alkanes incorporating the indole motif. In preliminary studies, several of these products showed biologically activity against cells from an array of human cancer cell lines. A mechanistic study was also carried out and suggested that the quinone methide might be the key intermediate. And in contrast to the conclusions of a previous report, the current work suggested that protonation by HFIP might not be the rate-determining step.