Fischer Tropsch’s reaction, known from 1925, receives special attention nowadays due to its key role in the CO2 or biomass valorization to liquid fuels and chemicals. Several aspects on the exact mechanism or the role of water in this reaction are not yet completely clear. Formyl species, HCO, have been proposed as the most probable reaction intermediate, but they have never been observed under operation conditions closed to the real ones. In this work, using DRIFTS-MS operando techniques, HCO intermediates are detected under a H2/CO flow and 200 °C. IR bands at 2900 cm−1 and 1440 cm−1 attributed to ν(C–H) and δ(HCO) vibrations modes characterize these species. Evolution of these bands with the reaction time evidences its high reactivity with OH groups, which explains the positive effect of water on the CO conversion previously observed.