In this paper, magnetic iron fibers of 3–10 μm diameter and an adjustable aspect ratio were synthesized successfully by a method involving pyrolysis of carbonyl under a magnetic field. A surface modification technology was also investigated. The electromagnetic parameters of the iron-fiber–wax composites were measured using the transmission/reflection coaxial line method in the microwave frequency range of 2–18 GHz. The results show that the prepared iron-fiber–wax composites exhibit high magnetic loss that can be further improved after phosphating. On the other hand, the complex permittivity was significantly decreased after phosphating. As a result, this kind of iron fiber may be useful for thin and lightweight radar-absorbing materials.