Densities and speeds of sound have been measured for the binary mixtures of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF 6 ] with ethylene glycol monoethyl ether (EGMEE), diethylene glycol monoethyl ether (Di-EGMEE), triethylene glycol monoethyl ether (Tri-EGMEE) over the whole composition range at atmospheric pressure. Experimental densities have been used to estimate excess molar volumes, V E . Changes in isentropic compressibility, Δκ s have been estimated by using experimental speed of sound and density values. Excess properties were fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors. The molecular scale interactions between ionic liquid and alkoxyalkanols have been investigated through 1 H NMR spectroscopy. NMR chemical shifts for hydroxyl group of alkoxyalkanols and their deviations show hydrogen bonding interactions of varying strengths between ionic liquid and alkoxyalkanol in their binary mixtures.