The microstructure and electromagnetic (EM) properties of four kinds of SiC fibers have been studied. These fibers are composed of amorphous SiCxOy, SiC nanocrystallines, free carbon, and nanopores, whose volume fractions are analyzed quantitatively. The content of free carbon notably affects the fiber's conductivity: the logarithm of conductivity increases linearly with the increase in the free carbon content when the volume fraction sum of free carbon and SiC exceed the percolation threshold. The EM loss mechanism is mainly composed of the conduction loss caused by free carbon and the polarization loss caused by SiC nanocrystallines. The content of free carbon is the decisive factor for the type of EM loss mechanism: the proportion of conduction loss increases linearly with the increase in free carbon content. Conduction loss is necessary for good EM absorption property, and polarization loss favors broadband absorption. For SiC fibers dominated by polarization loss, excellent absorption properties can be obtained in composites with higher fiber volume fraction (>20 vol%), which is crucial for structural absorbing materials.