Despite the increasing interest in radical-based fluoroalkylation techniques, the organofluorine compounds bearing the partially fluorinated hexafluoroisopropyl group remain extremely scarce due to the lack of appropriate reagents. Herein we report an unprecedented photoelectrocatalytic method for the C-H hexafluoroisopropylation of indoles and tryptophan peptides, utilizing the readily available hexafluoro-2-propanol (HFIP) as the fluoroalkylation reagent. In this process, HFIP is converted into hexafluoroisopropyl radicals, enabling fluoroalkylation reactions. This study broadens the potential applications of molecular photoelectrocatalysis, highlighting its capacity to enable transformations that are difficult to accomplish through traditional electrochemical or photochemical approaches.