Nanocomposite of CoFe2O4/SrFe12O19 has been synthesized by the electrospinning and calcination process. A novel method that cobalt powder was used to replace traditional cobalt salt in the precursor sol-gel for electrospinning was proposed. The crystal structures, morphologies, and magnetic properties of these samples have been characterized in detail. Moreover, when the average crystallite size of the hard/soft phases reached up to an optimal value, the CoFe2O4 have an enhanced saturation magnetization of 62.8 emu/g and a coercivity of 2,290 Oe. Significantly, the hysteresis loops for the nanocomposites show a single-phase magnetization behavior, and it has been found that the exchange coupling interaction strongly exists in the CoFe2O4/SrFe12O19 magnetic nanocomposite nanofibers.