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We investigated the microstructures and shape memory effect (SME) of cast Fe-Mn-Si-Cr-Ni alloys with four solidification modes, i.e., austenitic, austenitic-ferritic, ferritic-austenitic, and ferritic modes. Ferritic-austenitic and ferritic modes introduced more stacking faults than austenitic and austenitic-ferritic ones, reducing stress-induced critical martensite stress. Thus, the former solidification modes displayed better SME than the latter solidification modes.