The effect of B2O3 on crystallization behavior, structure, and heat transfer of CaO-SiO2-Na2O-B2O3-TiO2-Al2O3-MgO-Li2O fluorine-free mold fluxes was investigated using hot thermocouple technique (HTT), Raman spectroscopy, and infrared emitter technique (IET), respectively. The critical cooling rate in continuous cooling experiments decreased and the incubation time determined in isothermal experiments increased with increasing B2O3 content, both implying a decreasing crystallization tendency. The major phases of mold fluxes determined using X-ray diffraction changed from Ca2MgSi2O7 and Ca11Si4B2O22 to CaSiO3 with the increasing amount of B2O3. B2O3 increased the degree of polymerization in silicate network, forming 3D borate structures. Addition of B2O3 decreased the flux melting temperature which has a significant impeding effect on the crystal nucleation and growth. The heat flux of mold fluxes measured using IET showed that the increase of B2O3 from 4.7 to 6.8 mass pct impeded the heat flux; while a further increase of B2O3 from 6.8 to 10.4 mass pct promoted the heat transfer. This phenomenon was attributed to the variation of crystallization behavior and crystal morphology with different B2O3 content in the mold fluxes.