N-hydroxyethylpyridinium trifluoromethanesulfonate ([eOHpy][OTf]) and 2-phenylethyl alcohol (PEA) share similar structural characteristics. This study explored the variations in properties when 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][OTf]) was dissolved in them. Measurements of excess molar volume and viscosity showed that [emim][OTf]-[eOHpy][OTf] mixture exhibited ideal mixing behavior, whereas [emim][OTf]-PEA solution deviate significantly. 1H NMR spectra revealed a reversed chemical shift of hydroxyl groups in two mixtures, attributed to the presence of different hydrogen bond acceptors. In [emim][OTf]-PEA solution, competition between anions and hydroxyl groups as acceptors led to varying proportions of hydrogen bonds with solution concentrations. Conversely, in [emim][OTf]-[eOHpy][OTf] mixtures, hydrogen bonds mainly occurred between hydroxyl groups and anions, with minimal hydrogen bonds between hydroxyl groups. Molecular dynamics simulations demonstrated negligible changes in the solvation shell structure of ions in [emim][OTf]-[eOHpy][OTf] mixture but significant alterations in [emim][OTf]-PEA solution.