Four sugar-based chiral oxidovanadium(V) complexes [VO(L)(OMe)] (1), [VO(L5-NO2)(OMe)(MeOH)] (2), [VO(L5-OMe)(OMe)] (3), and [VO(L3-tBu)(OMe)(MeOH)] (4) have been synthesized. The crystal structures of complexes 1 and 2 could be determined by single crystal X-ray diffraction. Complexes 1 and 2 crystallize in the non-enantiogenic orthorhombic P212121 and monoclinic P21 space group, respectively. The structures reveal a difference in the coordination environment at the oxidovanadium(V) centers, where complex 1 is five-coordinate, while 2 is a six-coordinate complex with an additional coordinated methanol ligand. A comparison of the crystal structures of 1 and 2 shows that the vanadium(V) centers are present in different absolute configurations, despite crystallization from the same solvent. In fact, for complex 1, a C configuration at the chiral vanadium(V) center is found, which corresponds to a …