A crystalline 1:1 inclusion complex was isolated from the reaction of β-cyclodextrin (β-CD) with aqueous Cp2MoCl2. The existence of a true inclusion complex in the solid-state was confirmed by a combination of powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), FTIR and Raman spectroscopy, and magic-angle spinning (MAS) 13C NMR spectroscopy. Ab initio calculations were carried out to generate the possible inclusion geometries and calculate the vibrational frequencies for Cp2MoCl2 in the 100–400 cm−1 region. The best organometallic–β-CD interaction geometry was found to be one with one Cp ligand inside the host cavity. The vibrational spectra support the existence of this structure and in addition confirm that the organometallic is included with the MoCl bond intact. A crystalline 1:1 inclusion complex was isolated from the reaction of β-cyclodextrin with aqueous Cp2MoCl2 and characterized by powder X-ray diffraction, thermogravimetric analysis, FTIR and Raman spectroscopy, and magic-angle spinning 13C NMR spectroscopy. Ab initio calculations were performed to generate the possible inclusion geometries and calculate the vibrational frequencies.