Nanometer-sized gold nanoparticles have been prepared and surface-modified in order to stabilize alkane-in-water emulsions. A mixed hexane−undecanol ligand layer at the surface of the nanoparticles allowed us to tune their wettability and thus the adsorption at the oil−water interface. Oil droplets of the stable emulsions have been evidenced by confocal fluorescence microscopy, freeze-fracture transmission electron microscopy, and dynamic light scattering. Prepared emulsions were stable during performed cooling−heating cycles, in which the temperature stability of the emulsions has been studied by means of dynamic light scattering. The interfacial structure of the oil droplets was investigated by small-angle X-ray scattering. The obtained area per nanoparticle at the oil droplet interface was 30 nm2. The investigation of the nanoparticle adsorption at the curved interface of the emulsion droplets is in agreement with our previous study at a planar oil−water interface, in which the nanoparticles started to interact with each other at about the same area per particle.