SiC/SiN composite nanofibers with in situ embedded graphite, which show highly efficient electromagnetic (EM) wave absorption performance in gigahertz frequency, were prepared by electrospinning with subsequent polymer pyrolysis and annealing. By means of incorporating graphite and SiN into SiC, the EM wave absorption properties of the nanofibers were improved. The relationship among processing, fiber microstructure, and their superior EM wave absorption performance was systematically investigated. The EM wave absorption capability and effective absorption bandwidth (EAB) of nanofibers can be simply controlled by adjusting annealing atmosphere and temperature. The nanofibers after annealing at 1300 °C in Ar present a minimum reflection loss (RL) of -57.8 dB at 14.6 with 5.5 GHz EAB. The nanofibers annealed in N at 1300 °C exhibit a minimum RL value of -32.3 dB at a thickness of 2.5 mm, and the EAB reaches 6.4 GHz over the range of 11.3-17.7 GHz. The highly efficient EM wave absorption performance of nanofibers are closely related to dielectric loss, which originated from interfacial polarization and dipole polarization. The excellent absorbing performance together with wider EAB endows the composite nanofibers potential to be used as reinforcements in polymers and ceramics (SiC, SiN, SiO, AlO, etc.) to improve their EM wave absorption performance.