Direct or indirect electrochemical induction of S(RN)1 substitution of fluorinated aromatic or heteroaromatic halides is shown to be an efficient synthetic route to molecules of potential biological interest. 1-Iodo-2-trifluoromethyl benzene reacts, with the help of redox catalysts, with imidazole, 2-carboxaldehyde imidazole, 2-(4’-methoxyphenyl)imidazole and uracil ions, yielding the corresponding 5-(fluorinated-aryl)nitrogen bases. 1-(4’-Iodo-tetrafluorophenyl)imidazole reacts under direct or indirect electrochemical induction with 2-(4’-methoxyphenyl)imidazole, 2-carboxaldehyde imidazole, 2-methyl-5-nitro imidazole, uracil, adenine, hypoxanthine and xanthine ions leading to substituted-(2’,3’,5’,6’-tetrafluoro-4’-imidazol-1"-yl-phenyl) nitrogen bases.