Ag-doped Fe-based microspheres were synthesized via a one-pot solvothermal method, and displayed excellent mechanical stability and catalytic activity. Especially, the catalyst at Ag/Fe = 1 showed the lowest selectivity to CH₄ (12.6 wt%) and the highest to C_2–4 olefins (29.0 wt%), as well as a good selectivity to gasoline-range (C_5–11) fraction products (45.7 wt%). In addition, the catalytic activity and product selectivity of Ag/Fe measured at 280 °C was superior to that at 270 °C and 260 °C.