Fe-Based catalysts play crucial roles in Fischer-Tropsch synthesis (FTS). Herein, we for the first time demonstrate a facile sol-gel approach using natural magnetite and citric acid to fabricate porous Fe@C nanohybrids as FTS catalysts. Excellent FTS activity and stability were revealed and attributed to the formation of an Fe3C active phase and a core-shell structure. This flexible synthesis strategy clearly highlights the promising application of such materials in FTS.