Radical initiation for the perfluoroalkylation reaction of amino(hetero)aromatics has been accomplished employing the complex [(TMEDA)I·I₃] and visible light. This methodology circumvents the use of metal(organo)catalysts and biologically-relevant substrates are easily substituted with R_F moieties employing a mild and environmentally benign radical strategy starting from readily-available perfluoroalkyl iodides R_FI.