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Precipitated iron Fischer–Tropsch synthesis catalysts impregnated with chlorine were prepared and their Fischer–Tropsch synthesis performances were tested in a 1 L stirred tank reactor. The results showed that the chlorine modification had a significant influence on the Fischer–Tropsch synthesis performance of the precipitated iron catalyst. Compared with the catalyst without the chlorine modification, the catalyst containing about 0.1 wt% chlorine was deactivated by about 40% and the catalyst containing about 1 wt% chlorine was deactivated by about 65%. The textural properties, phase, reduction properties, and chlorine adsorption state of the catalysts before and after the Fischer–Tropsch synthesis were characterized. The strong interaction between chlorine and iron in the catalyst hindered the reduction and carbonization of the catalyst, which was the reason for the deactivation of the catalyst caused by the chlorine modification.