The effect of different heat treatment processes (as-cast, annealing, forging, and annealing after forging) on the microstructure transition and mechanical property evolution of Fe50Mn30Co10Cr10 alloys with different carbon contents (0, 0.2, 0.5 wt.%) was investigated, and a potential strengthening–toughening mechanism was revealed. With 0.5 wt.% carbon added, the interstitial carbon atoms provided a great deal of strength and the highest hardness was obtained. Meanwhile, the high carbon content generated a large amount of stacking fault energy and inhibited the transition of a face-centered cubic (FCC) to a hexagonal close-packed phase (HCP); as such, the TRIP and TWIP effects were induced during deformation and a favorable ductility with the largest elongation to fracture (of 141%) was achieved. The forged-annealed specimen with 0.2 wt.% carbon obtained favorable comprehensive mechanical properties, with an ultimate tensile strength of 795 MPa and an elongation of 104%. After forging, the grains were refined and several dislocations were generated; as such, the yield strength was greatly improved. With subsequent annealing, a good phase distribution of FCC and HCP was achieved, inducing the TRIP and TWIP effects during deformation and producing favorable ductility.