A detailed experimental analysis of reaction pathways proceeding in CO₂ hydrogenation over Fe-based catalysts was performed. The catalytic activity was measured at different degrees of conversion and used to analyze the production/consumption rates of reagents and products along the catalyst bed. It was demonstrated that except for the reverse water gas shift reaction and the subsequent hydrogenation of CO via Fischer-Tropsch (FT) mechanism, additional routes of hydrocarbon formation from CO₂ exist in the CO₂ hydrogenation. One of them is the methanation reaction which takes place over all studied catalysts. Another one is a direct pathway of C₂₊ hydrocarbon formation from CO₂ that plays a significant role at least for some catalysts. In this route, iron carbides may be responsible for hydrogenating CO₂ into C₂₊ hydrocarbons. Based on these results, the concept of requiring iron oxides as an essential active component for catalyzing the RWGS reaction in CO₂-FT should be reviewed.