Chiral aluminium complex are an inseparable part of the metal-based asymmetric transformations due to their high Lewis acidity, easy preparation, and high reactivity. To date, a variety of chiral aluminium complexes have been successfully developed and applied in many asymmetric reactions. The contents of this chapter are organised on the basis of the type of catalytic reaction. They include asymmetric cyanohydrin synthesis, Michael additions and sulfide oxidations. We also describe the applications of chiral aluminium complexes in miscellaneous reactions, such as Diels–Alder reactions, [3+2] cycloadditions, ene reactions, Strecker reactions, Reissert-type reactions, Meerwein–Ponndorf–Verley reductions, acyl halide–aldehyde cyclocondensations, aldol reactions, Pudovik reactions, Passerini-type reactions, radical additions, reductions, and copolymerisations.