Fischer-Tropsch synthesis was carried out over industrially important Fe/Cu/K/SiO2 catalysts containing a small amount of residual sodium which originated from the sodium carbonate solution used as a precipitating agent. The structural promoter, SiO2, was incorporated by two comparative sequences: immediately after precipitation (AP) or after a subsequent wash (AW). Whereas AW exhibited severe deactivation during the reaction, AP displayed high and stable catalytic activity for the entire reaction time. Furthermore, AP showed higher selectivity of liquid hydrocarbons, in particular heavy hydrocarbons, than AW. We attribute the advantageous catalytic performance observed in AP to the enhanced reducibility and higher surface basicity of AP, potentially induced by higher dispersion of catalysts and promoters.