The geometrically frustrated material-deuteroxyl cobalt chlorides Co2(OD)3Cl sample was first, to the best of our knowledge, successfully synthesized in the same single phase as the famous Co2(OH)3Cl, and their mid-infrared absorption spectra (4000-400cm–1) and Raman spectra (4000-95 cm–1) are first, to the best of our knowledge, measured respectively by FTIR spectroscopy and Micro-Raman spectroscopy to study the corresponding relationship between their spectral properties and crystal structure. Through the comparative analysis of the four spectra we definitely assign or tentatively suggest the vibration modes of hydroxyl/deuteroxyl groups in the trimeric hydrogen bond environment, (OH/D)–Co–(OH/D), and (H/D3···Cl)–Co–(Cl···H/D3). These results can be propitious to the low temperature spectral properties of Co2(OH)3Cl and Co2(OD)3Cl which must help to understand the underlying physics of their exotic geometric frustration phenomenon.