In this paper, mold simulator trials were firstly carried out to study the phenomena of the initial shell solidification of molten steel and the heat transfer across the initial shell to the infiltrated mold/shell slag film and mold. Second, a one-dimensional inverse heat transfer problem for solidification (1DITPS) was built to determine the temperature distribution and the heat transfer behavior through the solidifying shell from the measured shell thickness. Third, the mold wall temperature field was recovered by a 2DIHCP mathematical model from the measured in-mold wall temperatures. Finally, coupled with the measured slag film thickness and the calculations of 1DITPS and 2DIHCP, the thermal resistance and the thickness of liquid slag film in the vicinity of the meniscus were evaluated. The experiment results show that: the total mold/shell thermal resistance, the mold/slag interfacial thermal resistance, the liquid film thermal resistance, and the solid film thermal resistance is 8.0 to 14.9 9 10 À4 , 2.7 to 4.8 9 10 À4 , 1.5 to 4.6 9 10 À4 , and 3.9 to 6.8 9 10 À4 m 2 K/W, respectively. The percentage of mold/slag interfacial thermal resistance, liquid film thermal resistance, and solid film thermal resistance over the total mold/shell thermal resistance is 27.5 to 34.4, 17.2 to 34.0, and 38.5 to 48.8 pct, respectively. The ratio of radiation heat flux is around 14.1 to 51.9 pct in the liquid slag film.