Monoterpenoids are biogenic volatile organic compounds that play a major role in atmospheric chemistry by participating in the formation of aerosols. In this work, the monoterpenoid (R)‐(+)‐limonene oxide (C10H16O) was characterized in the gas phase by Fourier‐transform microwave spectroscopy in a supersonic jet. Five conformers of limonene oxide, four equatorial and one axial considering the configuration of the isopropenyl group, were unambiguously identified from analysis of the rotational spectrum. The observed conformers include cis and trans forms, which are stabilized by a subtle balance of hydrogen bonds, dispersive interactions, and steric effects. Estimated conformational relative abundances surprisingly reveal that the abundance of the axial conformer is similar to that of some of the equatorial conformers. In addition, the potential energy surface was extensively explored by using density functional theory and ab initio methods. Limonene oxide in the gas phase: Five conformers of limonene oxide, four equatorial and one axial considering the configuration of the isopropenyl group, are unambiguously identified in the gas phase by Fourier‐transform microwave spectroscopy. The axial conformer is, surprisingly, as abundant as some of the equatorial forms. The potential energy surface is extensively explored by using density functional theory and ab initio methods.