In order to gain microscopic insights into the extraction mechanism of strontium cations by 18-crown-6 (18C6) to room temperature ionic liquids (ILs), we simulated by molecular dynamics (MD) strontium complexes in neat ionic liquids and at their interfaces with water. We compared two ILs, based on the PF6- anion and either 1-butyl-3-methylimidazolium (C(4)min(+)) or 1-octyl-3-methylimidazolium (C(8)mim+) cations. Regarding the complexes, two states were considered: charged [Sr subset of 18C6](2+) vs neutral [Sr subset of 18C6,(NO3)(2)], where the nitrates are either fully dissociated or coordinated to Sr. In "dry" or "humid" [C(4)mim][PF6] and in "dry" [C(8)mim][PF6] IL, the neutral complex is found to be the most stable one. In the binary IL/water solutions, the charged complexes mostly partition to the aqueous phase, whereas the neutral [Sr subset of 18C6,(NO3)(2)] complexes are more concentrated in the interfacial domain. The aqueous solutions in contact with the ionic liquids contain C(4)mim(+), but almost no C(8)mim(+) ions, supporting a classical extraction mechanism to [C(8)mim][PF6] and an ion exchange mechanism to [C(4)mim][PF6]. Furthermore, remarkable events occurred during the dynamics, where complexes were extracted to the IL phases. When compared to the interfacial landscapes obtained with the same solutes at a classical organic liquid (chloroform)/water interface, those with ILs allow us to better understand specific features of liquid-liquid extraction to ILs.