Compared with Katsuki’s or Jacobsen’s catalysts (R,R,R,R)‐1 or (R,R)‐2, the phenomenon of reversed asymmetric induction in the course of the epoxidation of unfunctionalised olefins in the presence of (salen)manganese complex (S,S)‐3 is indirectly explained by means of quantumchemical calculations, as well as by 1H NMR spectra of salen ligand (S,S)‐10 and diamagnetic low‐spin nickel complex (S,S)‐7 and by its X‐ray structure analysis. Whereas in (R,R,R,R)‐1 and (R,R)‐2 the phenyl and cyclohexyl substituents occupy equatorial positions, the origin for the reversed enantioselection caused by manganese catalyst (S,S)‐3, is based on an axial position of the acyclic heteroalkyl substituents in the diimine backbone of (S,S)‐3 as exemplarily confirmed by model nickel complex (S,S)‐7. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)