An anion‐doped aluminium chlorofluoride AlCl0.1F2.8(OTeF5)0.1 (ACF‐teflate) was synthesized. The material contains pentafluoroorthotellurate (teflate) groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR‐IR spectra of adsorbed CD3CN reveal a blue‐shift of the adsorption band by 73 cm−1, which is larger than the shift for SbF5. Remarkably, ACF‐teflate catalyzes dehydrofluorination reactions of monofluoroalkanes to yield olefins in C6D6. In these cases, no Friedel‐Crafts products were formed.
