The method to determine the crystallinity of solid slag film is established by analyzing the DSC curve of solid slag film and corresponding quenched slag. The accuracy of the method is investigated by measurements of prepared samples whose crystallinity is given. In addition, the solid slag films of mold slags used to cast medium carbon steel and low carbon steel are obtained by heat flux simulator in laboratory, and the crystallinity of the two kinds of slag film are also measured by DSC method. Experimental results indicates that the crystallinity of solid slag film can be determined by comparing the crystallization enthalpy of solid slag film and corresponding quenched slag during heating process, and the relative error is within 5.03%. For medium carbon steel, the crystalline fraction of solid slag film is 88.6%, while the crystalline fraction of solid slag film corresponding to low carbon steel is 55.0%. The results are consistent with actual structure of solid slag films.