The effects of the ratio of precipitated SiO2 to binder SiO2 (Si(P)/Si(B)) on the reduction, carburization and catalytic behavior of precipitated Fe-Cu-K-SiO2 catalysts for Fischer-Tropsch synthesis (FTS) were investigated by N-2 physisorption, temperature-programmed reduction/desorption (TPR/TPD) and Mossbauer effect spectroscopy (MES). FTS performances of the catalysts were tested in a continuous stirred tank reactor (CSTR). It is found that the increase of Si(P)/Si(B) ratio (Si(P)/Si(B) = 0/25 similar to 15/10) decreases the crystallite size of the catalysts, improves the surface basicity, enhances the reduction and carburization of the catalysts, and increases the activity of the catalyst. However, when Si(P)/Si(B) ratio is further increased (Si(P)/Si(B) = 25/0), the catalyst exhibits a restrained reduction and carburization behavior, which may be attributed to the stronger metal-support interaction. Based on the present work, a catalyst with a suitable ratio of Si(P)/Si(B), for example Si(15)/Si(10) displays an optimal FTS performances.