The molecular interactions between the ionic liquid trimethylbutylammomium bis(trifluoromethylsulfonyl)imide, [N-1114][Tf2N], and three common solvents, including short chain alcohols (ethanol and 1-propanol) and an aprotic solvent (N,N-dimethylformamide or DMF) were investigated through experimental properties. The excess enthalpies were measured by calorimetry at temperatures from 308.15 K to 323.15 K over the whole composition range and excess volumes were calculated from density measurements. The vapor-liquid equilibrium (VLE) measurements of the [N-1114][Tf2N] + DMF mixture were obtained using a headspace gas chromatography instrument. It was determined that hydrogen bonds between the alcohol molecules contribute to the positive excess enthalpies, while the favorable interactions between DMF and [N-1114][Tf2N] might be explained by electrostatic interactions between the ionic liquid and the zwitterionic resonance structure of DMF. The nonrandom two liquid (NRTL) equation was successfully used to correlate the excess enthalpy and VLE results.