The weakly coordinating properties of the [Al(OTeF5)4]– anion were studied by the synthesis and characterization of its tetraalkylammonium salts [NAlk4][Al(OTeF5)4] [Alk4 = –(CH3)4, –(C2H5)4, –(C2H5)3CH3, –(C3H7)4, –(C4H9)4]. The one‐pot synthesis includes formation of the Brønsted acid in 1,2–difluorobenzene, H[Al(OTeF5)4](solv.), and its reaction with [NAlk4]Cl [Alk4 = –(CH3)4, –(C2H5)4, –(C2H5)3CH3, –(C3H7)4, –(C4H9)4] to the corresponding salts. Single crystals were obtained for [N(C4H9)4][Al(OTeF5)4] and characterized by X‐ray diffraction analysis.