The local structure and intermolecular dynamics of an equimolar mixture of benzene and 1,3-dimethylimidazolium bis[(trifluoromethane)sulfonyl]amide ([dmim][NTf2]) were studied using molecular dynamics (MD) simulations and femtosecond optical Kerr effect (OKE) spectroscopy. The OKE spectrum of the benzene/[dmim][NTf2] mixture at 295 K was analyzed by comparing it to an ideal mixture spectrum obtained by taking the volume-fraction weighted sum of the OKE spectra of the pure liquids. The experimental mixture spectrum is higher in frequency and broader than that of the ideal mixture spectrum. These spectral differences are rationalized in terms of the local structure around benzene molecules in the mixture and the intermolecular dynamics as reflected in the density of states from the MD simulations. Specifically, we attribute the deviation of the OKE spectrum of the mixture from ideal behavior to benzene molecules seeing a stiffer intermolecular potential due to their being trapped in cages comprised of ions in the first solvation shell.