The adduct free Lewis superacid Al(OCArF3)3 was obtained by the reaction of ArF3COH with AlEt3 and fully characterized (ArF = 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(OCArF)3] (Q+ = Cs+, Ag+, Tl+, [S(NMe2)3]+, [Ph3C]+, Li+, [NBu4]+, [FeCp2]+) and the chloride complex [Ph3C][ClAl(OCArF)3].