In this study, a set of thermodynamic, kinetic, and microstructure data is presented to simulate the non-equilibrium solidification of Fe-Al-Mn-Si-C alloys. The data were further validated with the experimental measurements and then used in a thermodynamic–kinetic software, IDS, to establish the effect of the alloying and cooling rate on the solidification behavior of high-AlMnSi (Al ≥ 0.5 wt pct, Mn ≥ 2 wt pct, Si ≥ 1 wt pct) steels. The modeling results were additionally validated by conducting electron probe microanalysis (EPMA) measurements. The results reveal that (1) solidification in high-AlMnSi steels occurs at much lower temperatures than in carbon steels; (2) increasing the cooling rate marginally lowers the solidus; (3) the microsegregation of Mn in austenite is much stronger than that of Si and Al due to the tendency of Al and Si to deplete from the liquid phase; (4) the residual delta ferrite content may be influenced by a proper heat treatment but not to the extent that could be expected solely from thermodynamic calculations; (5) in high-AlMnSi steels containing less than 0.2 wt pct carbon, the cracking tendency related to the strengthening above the solidus and the shell growth below the solidus may be much lower than in carbon steels.