Ionic liquids are a unique collection of liquid materials composed solely of ions. Under ambient conditions, room temperature ionic liquids (RTILs) stay as liquids, whereas conventional salts are in the crystalline state. Recently, we reported the self-assembly of solid particles in ionic liquid-in-water Pickering emulsions; the most intriguing observation is that some microparticles not only equilibrate at ionic liquid-water interfaces but are also extracted to the ionic liquid phase with high extraction efficiency. In this report, we discuss nanoparticle self-assembly at ionic liquid-water and ionic liquid-hexane interfaces using molecular dynamics (MD) simulations. The two systems show significantly difference in particle equilibrium positions, solid-liquid interaction, and interfacial ordering.