Deep-eutectic solvents (DESs) are regarded as alternative green solvents to ionic liquids. In this work we report the structural properties and hydrogen bonding (H-bonding) interactions of an aqueous DES system. The used DES, ethaline (ETH), is composed of choline chloride and ethylene glycol (EG) in 1 : 2 molar ratio. The investigations were carried out by FTIR spectroscopy combined with quantum chemical calculations. Excess spectroscopy and two-dimensional correlation spectroscopy (2D-COS) were used to explore the data in detail. The results showed that, upon mixing, ETH transforms to EG dimers and trimers and D 2 O clusters transform to various ETH-D 2 O complexes. Theoretical calculations show that water molecules insert between the anion and cation of ETH, break the strong doubly ionic Cl À … HÀ O Ch + H-bond, share charges of the ions and form H-bond with them, thus modulate the interaction properties of ETH. This study deepens our molecular-level understanding of the system and would shed light on its applications.