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In this study, we successfully prepared core–shell heterostructured nanocomposites (Fe NWs@SiO2), with ferromagnetic nanowires (Fe NWs) as the core and silica (SiO2) as the shell. The composites exhibited enhanced electromagnetic wave absorption and oxidation resistance and were synthesized using a simple liquid-phase hydrolysis reaction. We tested and analyzed the microwave absorption properties of Fe NWs@SiO2 composites with varied filling rates (mass fractions of 10 wt%, 30 wt%, and 50 wt% after mixing with paraffin). The results showed that the sample filled with 50 wt% had the best comprehensive performance. At the matching thickness of 7.25 mm, the minimum reflection loss (RLmin) could reach −54.88 dB at 13.52 GHz and the effective absorption bandwidth (EAB, RL < −10 dB) could reach 2.88 GHz in the range of 8.96–17.12 GHz. Enhanced microwave absorption performance of the core–shell structured Fe NWs@SiO2 composites could be attributed to the magnetic loss of the composite, the core–shell heterogeneous interface polarization effect, and the small-scale effect induced by the one-dimensional structure. Theoretically, this research provided Fe NWs@SiO2 composites with highly absorbent and antioxidant core–shell structures for future practical applications.