A series of chiral Schiff bases, 2,2′-bis(3-R1-5-R2-2-hydroxybenzylideneamino)-1,1′-binaphthyl H2L (R2= Cl, R1= Cl, Me, Et or NO2; R2= Me, R1= But; R2= NO2, R1= H, Me, Et, Pri, But or Cl), and their complexes [CuL1]1 and [Mn2L12(OMe)2]2(R1= R2= Cl) have been prepared. The crystal structure of the racemic form of 1 has been determined. Complex 1 is an active catalyst for the oxidation of alkenes by tert-butyl hydroperoxide. On the contrary, 2 is inert towards alkene epoxidation by PhIO. However, upon mixing Mn(O2CMe)3·xH2O and H2L in acetonitrile a green solution was obtained which could effect asymmetric epoxidation of alkenes by PhIO. The effects of the steric and electronic effects of the R1 and R2 substituents, temperature, and the addition of donors like N-methyl- and 2-methyl-imidazole and pyridine N-oxide on the catalytic activity of the MnIII+(S)-H2L systems towards alkene epoxidation have been investigated. When R1= Et and R2= NO2 the best enantiomeric excesses of 58 and 43% were found for epoxidation of cis-β-methylstyrene to (1S,2R)-cis-β-methylstyrene oxide and 4-chlorostyrene to 4-(S)-chlorostyrene oxide respectively.