FeNi alloy nanofibers have been prepared by an electrospinning process followed by air-calcination and H2 reduction to develop electromagnetic (EM) wave absorbers in the giga-hertz (GHz) frequency range. The thermal behavior and phase and morphology evolution in the synthetic processes were systematically investigated. Through the heat treatments of calcination and H2 reduction, as-spun PVP/FeNi precursor nanofiber has been stepwise transformed into nickel iron oxide and FeNi phases but the fibrous shape was maintained perfectly. The FeNi alloy nanofiber had the high aspect ratio and the average diameter of approximately 190 nm and primarily composed of FeNi nanocrystals with an average diameter of ~60 nm. The FeNi alloy nanofibers could be used for excellent EM wave absorbing materials in the GHz frequency range because the power loss of the FeNi nanofibers increased up to 20 GHz without a degradation and exhibited the superior EM wave absorption properties compared to commercial FeNi nanoparticles.