This work provided the first example of selective hydrodeoxygenation of 5‐hydroxymethylfurfural (HMF) to 2,5‐dimethylfuran (DMF) over heterogeneous Fe catalysts. A catalyst prepared by the pyrolysis of an Fe‐phenanthroline complex on activated carbon at 800 °C was demonstrated to be the most active heterogeneous Fe catalyst. Under the optimal reaction conditions, complete conversion of HMF was achieved with 86.2 % selectivity to DMF. The reaction pathway was investigated thoroughly, and the hydrogenation of the C=O bond in HMF was demonstrated to be the rate‐determining step during the hydrodeoxygenation, which could be accelerated greatly by using alcohol solvents as additional H‐donors. The excellent stability of the Fe catalyst, which was probably a result of the well‐preserved active species and the pore structure of the Fe catalyst in the presence of H2, was demonstrated in batch and continuous flow fixed‐bed reactors. Selective and stable Fe: Selective catalytic hydrodeoxygenation of 5‐hydroxymethylfurfural to 2,5‐dimethylfuran over heterogeneous Fe catalysts is demonstrated in batch and continuous flow fixed‐bed reactors. The Fe catalyst exhibited excellent stability, which is probably a result of the well‐preserved active species and the pore structure of the Fe catalyst in the presence of H2.