The behaviour of steels in the continuous casting process depends significantly on the steel composition, the associated phase transitions, and the corresponding thermophysical properties. Particularly "peritectic steels" , where the peritectic phase transformation (L + δ→γ + δ) coincides with the final solidification, are considered as critical and show a lower product quality. While the peritectic range is known exactly in the binary system Fe-C, the influence of alloying elements, such as Mn, Si, Al, and their combinations, are not completely clear. Therefore, the investigation of the effect of alloying elements on the peritectic phase transformation in steels is of particular importance. A practical evaluation of selected laboratory tests shows that the DynamicHeat-Flow-Differential-Scanning-Calorimetry (DSC) and High-Temperature-Laser-Confocal-Microscopy (HT-LSCM) enables a clear identification of peritectic steels. Selected ternary and quaternary Fe-C systems were investigated based on model alloys by means of systematic DSC measurements. The findings on the effect of Al and the interaction of Si with Mn with respect to the Fe-C system represent a new scientific ground.