The dimethylchloronium salt [Me2Cl][Al(OTeF5)4] is used to methylate electron‐deficient aromatic systems in Friedel–Crafts type reactions as shown by the synthesis of N‐methylated cations, such as [MeNC5F5] , [MeNC5F4I] , and [MeN3C3F3] . To gain a better understanding of such fundamental Friedel–Crafts reactions, the role of the dimethylchloronium cation has been evaluated by quantum‐chemical calculations.