We report the spontaneous formation of emulsion droplets and multilamellar concentric onions when a water drop is immersed into dodecane containing phospholipids. We show that the origin of the spontaneous emulsification is the formation of a semierystalline multilamellar film at the dodecane-water interface, which swells with water, shedding the emulsion and onion droplets. We use coherent anti-Stokes Raman scattering microscopy to determine that the shell of the onion structures is composed of partially hydrated concentric bilayers, and the core is composed of lipids, water, and dodecane.