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The effects of Ni content and heat-treatment process on the toughness of a super ferritic stainless steel with 26 wt% Cr and 3.5 wt% Mo were investigated. It was found that with the increase of Ni content, the Charpy impact toughness improved remarkably, and transformed from cleavage brittle fracture to the most ductile fracture. There were no obvious differences between the high- and low-Ni contents on the microstructure and mechanical properties since the addition of Ni did not influence crystal structure, phase composition, and precipitation of ultra pure ferritic stainless steels. Meanwhile, the heat-treatment process was a key point to maintain a high level of toughness by optimizing structure and removing detrimental precipitation, i.e., chi phase.