High-resolution molybdenum K-edge X-ray emission spectroscopy (XES) was used to characterize the K beta(4) and K beta '' valence-to-core transition bands in the oxo-Mo compounds K2MoO4, MOO(S-2-CNEt2)(2), and MoO2(S2CNEt2)(2). The K beta(4) and K beta '' emission bands are attributed to transitions to the Mo 1 s core hole from molecular orbitals possessing primarily molybdenum 4d and oxygen 2s character, respectively. This communication describes the first assignment of the K beta '' interatomic band in the emission spectra of molybdenum complexes. Additionally, the K beta(4) and K beta '' transitions are shown to be sensitive to the chemical and electronic environment of the metal, suggesting that high-resolution XES might be an effective method for elucidating the nature of the molybdenum centers in biological systems.