Molybdenum complexes with ONO tridentate Schiff base ligands based on salicylideneaminophenolato (SAP) backbone with OH substitution on the salicyl arene ring have been synthesized and characterized. The molecular structures of the full series of OH substituted molybdenum complexes were determined by X-ray crystallography as monomers stabilized by one solvent molecule, [MoO2L(D)]. All dimeric complexes [MoO2L]2 were tested for the epoxidation of cyclooctene and cyclohexene under organic solvent-free conditions using aqueous TBHP as oxidant. The position of the OH on the SAP-modified ligand influenced the catalytic activity of the respective complexes. DFT calculations for the catalytic cycle yield energy spans in agreement with the experimentally observed activity trend.