The interfacial structure in a liquid crystal/nanoparticle nanocomposite is dictated by the type of nanoparticle and its functionalization compound. Nanocomposites consisting of smectic liquid crystals and nanoparticles have been studied for their applications in devices such as photovoltaics and to model biological devices. With the use of a model system, this paper presents evidence of an interfacial structure close to the vicinity of the nanoparticles that is more disordered than that of the bulk liquid crystal but is still in the smectic phase, and it seems to follow the faceting of the structure the nanoparticles adopt when they coalesce or recluster after the liquid crystal is added.