A new octahedral titanium binaphthyl-bridged Schiff base complex (1) was synthesized and characterized. Analysis by H-1 and C-13-NMR spectroscopy and X-ray crystallography indicated that the C-1-symmetric cis-beta isomer is preferentially formed as one of the two possible enantiomeric couples of diasteroisomers. The catalytic behaviour of the complex 1 toward epoxidation of allylic alcohols was investigated. Using only 0.5% mol of the complex 1 the epoxyalcohols are obtained in very high regio-, chemo- and diastercoselctive way by the MW exposure of the mixture in solvent free-conditions. (c) 2005 Elsevier B.V. All rights reserved.