MoVI complexes with novel ditopic diaminotetraphenol ligands have been prepared by using a one-pot procedure in methanol or DMSO with [MoO2(acac)2] (acac = acetylacetonate) as the molybdenum source. The complexes were characterised with X-ray diffraction, NMR spectroscopic studies, elemental analysis and IR spectroscopy. In the solid state, the compounds represent either a rodlike molecular or oxido-bridged polymeric structure. The catalytic activity of the complexes was investigated by oxidising benzyl alcohol and 1-phenylethanol with hydrogen peroxide to the corresponding aldehyde and ketone, respectively. Furthermore, the catalytic activity was surveyed also in epoxidation of cyclooctene.