We report the synthesis and characterization of several amino alcohol-derived reduced Schiff base ligands (AORSB) and the corresponding (VO)-O-IV and V-V complexes. Some of the related Schiff base variants (amino alcohol derived Schiff base = AOSB) were also prepared and characterized. With some exceptions, all compounds are formulated as dinuclear compounds {(VO)-O-IV(L)}(2) in the solid state. Suitable crystals for X-ray diffraction were obtained for two of the AORSB compounds, as well as a rare X-ray structure of a chiral (VO)-O-IV compound, which revealed a dinuclear {(VO)-O-IV(AOSB)}(2) structure with a rather short V-V distance of 3.053(9) angstrom. Electron paramagnetic resonance (EPR), V-51 NMR, and density functional theory (DFT) studies were carried out to identify the intervenient species prior to and during catalytic reactions. The quantum-chemical DFT calculations were important to determine the more stable isomers in solution, to explain the EPR data, and to assign the V-51 NMR chemical shifts. The V(AORSB) and V(AOSB) complexes were tested as catalysts in the oxidation of thioanisole, with H2O2 as the oxidant in organic solvents. In general, high conversions of sulfoxide were obtained. The V(AOSB) systems exhibited greater activity and enantioselectivity than their V(AORSB) counterparts. Computational and spectroscopic studies were carried out to assist in the understanding of the mechanistic aspects and the reasons behind such marked differences in activity and enantioselectivity. The quantum-chemical calculations are consistent with experimental data in the assessment of the differences in catalytic activity between V(AOSB) and V(AORSB) peroxido variants because the V(AORSB) peroxido transition states correspond to ca. 22 kJ/mol higher energy activation barriers than their V(AOSB) counterparts.