© 2020 American Chemical Society. The rotational dynamics of carbon monoxide (CO) in ionic liquids (ILs) was investigated by nuclear magnetic resonance (NMR) relaxation measurements and molecular dynamics (MD) simulations. NMR spin−lattice relaxation time measurements were performed for 17O-enriched CO in 10 ILs (four imidazolium-cation-based, four phosphonium-cation-based, and two ammonium-cation-based ILs, all paired with the bis(trifluorosulfonylmethane)imide anion). In combination with previously reported data for five ILs and viscosity data, our results indicated that the obtained rotational relaxation times (τ2R) were much smaller than those predicted using the Stokes−Einstein− Debye (SED) theory. For the same viscosity/temperature values, the τ2R−1 value increased linearly with increasing carbon number of the alkyl group in the cation. The deviation from the SED equation was due to the insensitivity of τ2R to the carbon number, even though a higher carbon number generally leads to higher viscosity values for ILs. To investigate the unique rotational properties of CO in the ILs, MD simulations were performed on five representative ILs (two imidazolium, two phosphonium, and one ammonium) containing CO solutes. From rotational correlation function analyses, the CO rotation mainly occurred in a free rotation-like manner within 1 ps, which explained the relative insensitivity of CO rotation to viscosity. In the subsequent time scale (>1 ps), the minor component of the CO rotation was discriminated among different ILs. It was strongly suggested that, because CO preferably locates in the outer part of the alkyl groups in the cation, the slow CO rotation is correlated with the outer alkyl dynamics, which are decoupled from the whole cation rotation.