The dynamic thermal analysis method and specially designed experiment device are used to determine the liquidus and solidus temperatures of LaF3-LiF molten salts in different compositions. Based on the determined results and under the assumed conditions of only one single La species in the molten salts and the formation of the La-F ion in accordance with Temkin or Flood model, the structural ions of LaF3-LiF molten salts in which the mole fraction of LaF3 was less than 15% were studied by cryoscopic method. The results show that the most reasonable dissociation reaction mechanism of LaF3 in LaF3-LiF melts in which LaF3 mole fraction is less than 15% is LaF3+F-=LaF4-.