A photocatalytic reactivity platform for the C2-trifluoroethylation and perfluoroalkylation of 3-substituted indoles has been developed. A range of fluoroalkyl halides have been employed as radical precursors under mild, transition-metal-free conditions to access new (per)fluorinated chemical space featuring the indole substructure. This general protocol is also applicable to indole-containing peptides.