Abstract In this work we report the structural and spectroscopic characterization of the bulk MoS_xSe_2-x solid solutions synthesized by chemical vapor transport. The bulk crystals were analyzed by scanning electron microscopy (SEM), x-ray diffraction (XRD), energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Electron microscopy evaluation of the layered materials shows two distinct types of crystals: flat and easily cleavable hexagonal microcrystals up to 50 μm in size, and agglomerated irregular crystals of 5–10 μm in size. XRD shows a consistent increase in interplanar spacing as the Se content is increased in the sample series. Raman spectra of bulk MoS_xSe_2-x obtained with three different excitation energies revealed first order phonon modes associated with pure MoS₂ (x = 2) and MoSe₂ (x = 0) along with a complex behavior of vibrational modes when x had intermediate values. XPS Mo_3d line scans indicate a slight shift towards lower binding energies as the Se/S ratio increases, consistent with the expected energies of MoSe₂. A simple and direct relationship can be established between the characteristic Raman peaks and the value of x, which can be useful for identifying the compositions of TMD crystals.