Solvation structure of glucose in 1-ethyl-3-methylimidazolium methylphosphonate, [C2mIm+][CH3(H)PO3-] ionic liquids and liquid structure of the neat [C2mIm+][CH3(H)PO3-] were investigated by high-energy X-ray diffraction (HEXRD) experiments with the aid of molecular dynamics (MD) simulations. In neat [C2mIm+][CH3(H)PO3-], a specific interaction between cation and anion is found, i.e., the oxygen atoms within CH3(H)PO3- are hydrogen bonded with the hydrogen of C2 position within C2mIm+. In glucose/[C2mIm+][CH3(H)PO3-] solutions, a significant peak is observed at 2.6 Å in experimental radial distribution function and is enhanced with increasing glucose concentration. It is found from MD simulations that the peak is originated from the nearest neighbor intermolecular interaction between glucose and anion in [C2mIm+][CH3(H)PO3-]. The atom-atom pair correlation function derived from MD results shows that hydroxyl groups of glucose interact with oxygen atoms within CH3(H)PO3- through the hydrogen bonds. The intermolecular hydrogen bonds coexist with the intramolecular hydrogen bond in a glucose molecule. We conclude that glucose is easy to form hydrogen bond with polar CH3(H)PO3 anion, however, rupture of intramolecular hydrogen bonds within glucose is not enough in the ionic liquid.