The first example of the α-ferrocenylalkylation reaction of substituted 2-thiohydantoin was performed using a developed two-step procedure involving the formation of a salt of the starting thioamide with (ferrocenylmethyl) trimethyl ammonium, followed by alkylation of the anion by its counterion. The reaction results in the formation of isomeric <em>N</em>- and <em>S</em>-alkylation products; moreover, <em>N</em>-alkylation of the thiohydantoin anion in the presence of a more nucleophilic sulfur atom is observed for the first time. The resulting compounds are promising organometallic ligands for the synthesis of bimetallic complexes.