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Deep Eutectic Solvents (DESs) are gathering growing attention as sustainable solvents in different fields ranging from synthesis to electrochemical devices. Albeit DES are widely employed, the fundamental knowledge on their interspecies relations is still partial. Understanding the chemistry of this class of green solvent is an essential step to further tune their properties. In this study, we report a detailed experimental and theoretical investigation of two choline-chloride glycerol mixtures using electrochemical, spectroscopic (Raman/Far Infrared), diffraction (X-ray) and molecular simulation methods. Remarkably different Far-infrared spectra have been surprisingly collected for the two mixtures. Differences are attributed to the deconstruction of the extended hydrogen bond network characteristic of pure glycerol and of the 1:2 mixture and absent in the glycerol-richer mixture 1:3. From the analysis of X-ray profiles, that are very well reproduced by molecular dynamics, it was found that the lack of the glycerol H-bond interactions in the glycerol-richer mixture (Ch:Gly 1:3) can be attributed to the establishment of a full coordination shell of polyalcohol molecules around the chloride anion. In the 1:2 composition the coordination is probably defective, as signaled by the FIR spectrum that significantly maintains the features observed for the precursor glycerol, and the chloride stabilization is ensured by interaction with both choline hydroxyl and electrostatic interactions.