The phenomenon of supercooling in metals—that is, the preservation of a disordered, fluid phase in a metastable state well below the melting point1—has led to speculation that local atomic structure configurations of dense, symmetric, but non-periodic packing act as the main barrier for crystal nucleation2, 3. For liquids in contact with solids, crystalline surfaces induce layering of the adjacent atoms in the liquid4, 5 and may prevent or lower supercooling6. This seed effect is supposed to depend on the local lateral order adopted in the last atomic layers of the liquid in contact with the crystal. Although it has been suggested that there might be a direct coupling between surface-induced lateral order and supercooling6, no experimental observation of such lateral ordering at interfaces is available6. Here we report supercooling in gold-silicon (AuSi) eutectic droplets, enhanced by a Au-induced (6×6) reconstruction of the Si(111) substrate. In situ X-ray scattering and abinitio molecular dynamics reveal that pentagonal atomic arrangements of Au atoms at this interface favour a lateral-ordering stabilization process of the liquid phase. This interface-enhanced stabilization of the liquid state shows the importance of the solid–liquid interaction for the structure of the adjacent liquid layers. Such processes are important for present and future technologies, as fluidity and crystallization play a key part in soldering and casting, as well as in processing and controlling chemical reactions for microfluidic devices or during the vapour–liquid–solid growth of semiconductor nanowires.