The interfacial structure between the room-temperature ionic liquid, 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIM+/PF6−) and rutile (110) surface is simulated by classical molecular dynamics simulation, aiming to model a crucial constituent of the electrolyte/semiconductor interface. The simulation results show several enhanced layers forming in the interfacial region, especially for the anions. A well ordered double layering structure of the ions is also observed in the interfacial region. The cations are found to organize themselves in a parallel alignment with respect to the TiO2 slab, with an obvious elongation of the side chains.