Fe-Mn-C-Al alloy is a new steel grade of TWIP steel developed in recent years. It has an excellent combination of elongation and tensile strength, as well as good anti-delayed fracture property. However, the crack sensitivity of this new TWIP steel has not been reported yet. In this study, differential thermal analysis (DTA) method was used, combined with professional thermodynamic software ThermoCalc to analyze the solidification behavior for Fe-Mn-C-Al alloys with different chemical compositions. Based on this, the crack sensitivity of TWIP steel is further determined. Through this study, it was found that Fe-Mn-C-Al TWIP steel may have a solidification sequence with high crack sensitivity, belonging to hypo-peritectic steel. Moreover, it was found that the carbon content has a large influence on the solidification behavior, and the manganese content also affects the solidification sequence. It can make the phase transition sequence of the solidification process change significantly, which may avoid the solidification behavior of hypo-peritectic reaction. The analysis results by thermodynamic software ThermoCalc are in good agreement with the experimental results. It displays thermoCalc can be a cost-effective way to develop Fe-Mn-C-Al TWIP steel. It is of great significance for shortening the development period of new Fe-Mn-C-Al steel grades.