Blue LEDs-irradiation of a mixture of N,N,N´,N´-tetramethylethylenediamine (TMEDA) and perfluoroalkyl iodides (RF-I) -Electron Donor Acceptor (EDA)-complex- in the presence of triphenylamines (TPAs) in an aqueous solvent mixture afforded mono-perfluoroalkylated triphenylamines (RF-TPA) in good yields. These RF-TPA were further subjected to acetone-sensitized [6π]-electrocyclization at 315 nm-irradiation affording exclusively perfluoroalkylated endo-carbazole derivatives (RF-CBz) in quantitative yields. Mechanistic studies and photophysical properties of products are studied.