The adduct free Lewis superacid Al(OCArF3)₃ was obtained by the reaction of ArF3COH with AlEt₃ and fully characterized (Ar^F = C₆F₅). It comprises a high thermal stability up to 180 °C and a distinct reactivity towards Lewis bases, as exemplified by the isolation of the neutral adducts Al(OCArF3)·D (D = MeCN, THF, Et₂O, pyridine, OPEt₃), the fluoride complexes [Q][FAl(OCAr^F)₃] (Q⁺ = Cs⁺, Ag⁺, Tl⁺, [S(NMe₂)₃]⁺, [Ph₃C]⁺, Li⁺, [NBu₄]⁺, [FeCp₂]⁺) and the chloride complex [Ph₃C][ClAl(OCAr^F)₃].