Rare earth have been widely used in the heavy rail steels to improve the impact toughness, yield strength, and high-temperature plasticity by deforming inclusions and refining grains. However, amounts of rare earth oxides with high melting temperatures can be generated and enter the mold fluxes, which has a significant influence on the lubrication and the heat transfer capability of mold fluxes and even the smooth of the continuous casting process. Thus in this work, effects of different CeO 2 contents on melting temperature, viscosity, and structure of the CaF 2-bearing mold fluxes and the B 2 O 3-containing mold fluxes for casting the rare earth alloy heavy rail steels were investigated systemically. Besides, the mechanisms of the viscosity and structure were discussed. Results show that CeO 2 increases the melting temperature and decreases the viscosity at high temperature of both two mold fluxes. The break temperature of the CaF 2-bearing mold fluxes increases heavily with the addition of CeO 2. Analyses of Raman spectra and the 11 B magic angle spinning nuclear magnetic resonance spectra (11 B MAS NMR) show that CeO 2 enhances the de-polymerization of the network structure of two mold fluxes, leading to the decrease of viscosity at each temperature.