A simple and modulable access to a structural variety of enantiopure amino-substituted ferrocenylsulfoxides and their use as chiral catalysts in the asymmetric addition of diethylzinc to aromaticaldehydes is described. Moderate to high enantioselectivities (up to 96% ee) were obtained in thecase of the arylsulfonamide ligands (RFc, RS)-4h and (RFc, RS)-4i. It has been demonstrated thatthe planar chirality of the ferrocene unit is the decisive chiral element involved in the reaction.