Fischer-Tropsch synthesis provides an important opportunity for utilization of biomass and plastic waste. Iron catalysts are the catalysts of choice for light olefin synthesis using Fischer-Tropsch reaction. In this paper, we investigate strong promoting effects of antimony and tin on the catalytic performance of silica supported iron Fischer-Tropsch catalysts using a combination of advanced and in-situ techniques. The catalyst doping with these elements added via impregnation results in a major increase in the reaction rate and much better catalyst stability. No enhancement of iron dispersion was observed after the promotion, while somewhat higher extent of iron carbidization was observed in the antimony promoted catalysts. Iron-bismuth bimetallic nanoparticles are detected by several techniques. In the working catalysts, the promoters are located in close proximity to the iron nanoparticles. The promotion leads to the 7–10 times increase in the intrinsic activity of iron surface sites due to their interaction with the promoters.