The thermal stability and atomic structure of the solid-liquid interface of lithium iron nanoalloys with rhombohedral configuration are examined by embedded atom method and molecular dynamics. The thermal stability of pure Li and Fe rhombohedral nanoparticles are initially evaluated. The calculated melting points for nanoparticles have a good linear relationship with nanoparticle size, and the extrapolated bulk melting temperatures of the two metals are consistent with experimental values. For Li-Fe nanoalloys, the calculated radial distribution function and atomic configuration show that Li atoms at the interface between Li and Femaintain an ordered arrangement when temperature is larger than melting point. The melting temperature of Li shell reduces with increased Li atoms in the Li-Fe nanoalloy. The conclusion can be attributed to the structured order at the solid-liquid interface. When the total amount of Li increases, the Fe core decreases in size and the number of Li atoms in contact with Fe at the interface is lesser, which leads the melting temperature of the Li shell decreases when the total amount of Li atoms increases in the particle. (C) 2015 Published by Elsevier B.V.