X-ray absorption spectra have been measured at the S K-, Cl K-, and Mo L3- and L2-edges for the d 0 dioxomolybdenum(VI) complexes LMoO2(SCH2Ph), LMoO2Cl, and LMoO2(OPh) (L ) hydrotris(3,5- dimethyl-1-pyrazolyl)borate) to investigate ligand -metal covalency and its effects on oxo transfer reactivity. Two dominant peaks are observed at the S K-edge (2470.5 and 2472.5 eV) for LMoO2(SCH2Ph) and at the Cl K-edge (2821.9 and 2824.2 eV) for LMoO2Cl, demonstrating two major covalent contributions from S and Cl to the Mo d orbitals. Density functional calculations were performed on models of the three Mo complexes, and the energies and characters of the Mo 4d orbitals were interpreted in terms of the effects of two strong cis-oxo bonds and additional perturbations due to the thiolate, chloride, or alkoxide ligand. The major perturbation effects are for thiolate and Cl - ﷿ mixed with the dxz orbital and U mixed with the dz 2 orbital. The calculated 4d orbital energy splittings for models of these two major contributions to the bonding of thiolate and Cl ligands (2.47 and 2.71 eV, respectively) correspond to the splittings observed experimentally for the two dominant ligand K-edge peaks for LMoO2(SCH2Ph) and LMoO2Cl (2.0 and 2.3 eV, respectively) after consideration of final state electronic relaxation. Quantification of the S and Cl covalencies in the d orbital manifold from the pre-edge intensity yields, 42% and 17% for LMoO2(SCH2Ph) and LMoO2Cl, respectively. The Mo L2-edge spectra provide a direct probe of metal 4d character for the three Mo complexes. The spectra contain a strong, broad peak and two additional sharp peaks at higher energy, which are assigned to 2p transitions to the overlapping t2g set and to the dz 2 and dxy levels, respectively. The total peak intensities of the Mo L 2- edges for LMoO2(OPh) and LMoO2Cl are similar to and larger than those for LMoO2(SCH2Ph), which agrees with the calculated trend in ligand-metal covalency. The theoretical and experimental description of bonding developed from these studies provides insight into the relationship of electronic structure to the oxo transfer chemistry observed for the LMoO2X complexes. These results imply that anisotropic covalency of the Mo- Scys bond in sulfite oxidase may promote preferential transfer of one of the oxo groups during catalysis.