Imidazole has gained attention as an alternative to anhydrous proton conductor in high-temperature proton exchange membrane fuel cells. A detailed investigation of proton propensity and the orientation of the imidazolium cation at the liquid-vacuum interface is important for understanding the interfacial properties of imidazole-based proton-conductive materials. Here, we perform all-atom molecular dynamics simulation on a slab model of the liquid imidazole-vacuum interface. Proton transportation process between the imidazolium cation and neutral imidazole molecules is described by the multistate empirical valence bond model of imidazole developed previously. The imidazolium cation shows a tendency to stay in the bulk region rather than at the outermost surface, and the NN vectors and norm vectors of both the imidazolium cation and imidazole molecules are more probable to be perpendicular to the surface normal vector at the interface than in the bulk. The orientation of the hydrogen bond cluster shows the same tendency as the NN vectors, which indicates that proton transportation along the direction of the surface normal vector is hindered. The instantaneous surface analyses show that the fluctuation is depressed when the imidazolium cation is near the outermost surface, which makes it less favorable for the cation appearing at the interface.