Carbon/manganese ferrite (C/MnFe2O4) composite nanofibers were fabricated using electrospinning technique followed by carbonization process under mixed of air and argon atmosphere at 400, 600 and 800°C, respectively. The prepared composite nanofibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM) and X-ray absorption spectroscopy (XAS) including X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). After calcination at 800°C, the composite nanofibers of C/MnFe2O4 were obtained with a mean diameter of nanofibers of approximately 700–800nm. The structure of MnFe2O4 was successfully studied using XAS technique and was found to be cubic spinel with a coupling of Mn2/Mn3+ and Fe3+ oxidation states. All composite nanofibers exhibited ferromagnetic behavior especially after being calcined at 800°C. This ferromagnetic properties were related to the distribution of cations over tetrahedral and octahedral sites as revealed by EXAFS results.