Fischer-Tropsch synthesis (FTS) that converts syngas into long-chain hydrocarbons is a key technology in the chemical industry. As one of the best catalysts for FTS, the Fe-based composite develops rich solid phases (metal, oxides, and carbides) in the catalytic reaction, which triggered the quest for the true active site in catalysis in the past century. Recent years have seen great advances in probing the active-site structure using modern experimental and theoretical tools. This Perspective serves to highlight these latest achievements, focusing on the geometrical structure and thermodynamic stability of Fe carbide bulk phases, the exposed surfaces, and their relationship to FTS activity. The current reaction mechanisms on CO activation and carbon chain growth are also discussed, in the context of theoretical models and experimental evidence. We also present the outlook regarding the current challenges in Fe-based FTS.