Abstract: In-situ DRIFTS and chemical trapping techniques were employed to investigate the adsorbed species over the surface of precipitated iron-based catalysts and the mechanism of oxygenates formation in high temperature Fischer-Tropsch synthesis. The results showed that both linear and bridged CO molecules are present on the catalyst surface, which leads the formation of numerous oxygenated precursors. Some crucial surface intermediates are detected by the in-situ DRIFTS, such as acetate, acetyl and methoxide. The surface of precipitated iron-based catalysts is characterized by following facts: (ⅰ) alcohols are able to react with free surface hydroxyls to form alkoxy species; (ⅱ) surface adsorbed molecules exhibit certain oxidizing ability; (ⅲ) basic sites such as OH- and lattice oxygen may react with CH₃OH or CH₃CHO molecules. By chemical trapping of the CH₃OH + CO and CH₃I + CO + H₂ reactions, it was found that acetyl is an important intermediate for oxygenates and the hydrogenation of acetyl is a crucial step for the formation of oxygenates. On the basis of these observations, the mechanism of oxygenates formation in high temperature Fischer-Tropsch synthesis over the precipitated iron-based catalysts was then proposed.