The effects of Zr and K promoters on the structure, adsorption, reduction, carburization and catalytic behavior of precipitated iron-based Fischer-Tropsch synthesis (FTS) catalysts were investigated. The catalysts were characterized by N-2 physisorption, temperature-programmed reduction/desorption (TPR/TPD) and Mossbauer effect spectroscopy (MES) techniques. As revealed by N-2 physisorption, Zr and/or K promoted catalysts showed lower surface area than Fe/SiO2 catalyst. Zr promoter inhibited the reduction and carburization because of the interaction between Fe and Zr in Fe-Zr/SiO2 catalysts. K promoter enhanced the reduction in CO and apparently facilitated the CO adsorption, thus promoted the carburization, but it retarded the reduction in H-2 and severely suppressed the H-2 adsorption. Compared with the singly promoted catalysts, the doubly promoted catalyst had the highest FTS activity. In addition, both Zr and K promoters suppressed the formation of methane and shifted the production distribution to heavy hydrocarbons.