The valence tautomeric stated of Co(phen)-(3,5-DBQ)(2) and co(tmeda)(3,5-DBQ)(2), where 3,5-DBQ is either the semiquinone (SQ(-)) or catecholate (Cat(2-)) form of 3,5-di-tert-butyl-1,2-benzoquinone, have been examined by a series of cobalt-specific X-ray spectroscopies. In this work, we have utilized the sensitivity of 1s3p X-ray emission Spectroscopy (K beta XES) to the oxidation and spin states of 3d transition-metal ions to determine the cobalt-specific electronic structure of valence tautomers. A comparison of their K beta XES spectra with the spectra of cobalt coordination complexes with known oxidation and spin states demonstrates that the low-temperature valence tautomer can be described as a low-spin Co-III configuration and the high-temperature valence tautomer as a high-spin Co-II configuration. This conclusion is further supported by L-edge X-ray absorption spectroscopy (L-edge XAS) of the high-temperature Valence tautomers and ligand-field atomic-multiplet calculations of the K beta XES and L-edge XAS spectra. The nature and strength of the magnetic exchange interaction between the cobalt center and SQ(-) in cobalt valence tautomers is discussed: in view of the effective spin at the Co site from K beta XES and the molecular spin moment from magnetic susceptibility measurements.