The structure and microwave magnetic performance of Fe, Fe-Si-C, and Fe-Co-Si-C powders fabricated by mechanical milling has been studied. The study was aimed at revealing of the effect of shape, composition, and structure of the powder particles on the microwave frequency dispersion of permeability of the powder-filled composites in the frequency range of 0.1−3 GHz. At low frequencies, below 1 GHz, the main reason causing the differences in the microwave magnetic properties of the powders is the shape of powder particles. At higher frequencies, the magnetic performance is mainly due to the effect of eddy currents and is determined by the size of powder particles. The difference in the composition of the powders under study and, therefore, corresponding differences in intrinsic permeability of these have a minor effect on the microwave magnetic performance as compared to the effects of particle size and shape.