In the present work, Fe-montmorillonite (Fe-MMT) was synthesized by hydrothermal method, and then was modified by cetyltrimethyl ammonium bromide (CTAB). The polyamide6 (PA6)/organic-modified Fe-montmorillonite (Fe-OMT) composite nanofibers were prepared by facile compounding and electrospinning. Fe-OMT was first dispersed in N, N-dimethyl formamide and then compounded with PA6 which was dissolved in formic acid. The composite solutions were electrospun to form PA6/Fe-OMT composite nanofibers. The structure, morphology, thermal stability, and crystalline properties of the composite nanofibers were characterized by Fourier transfer infrared (FTIR) spectra, Energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), High-resolution electron microscopy (HREM), Scanning electron microscopy (SEM), and Thermogravimetric analyses (TGA), respectively. It was found that the silicate clay layers were well exfoliated within the composite nanofibers and were oriented along the fiber axis. The SEM images indicated that the loading of Fe-OMT decreased the diameters of composite nanofibers. TGA analyses revealed that the thermal stability was notably improved in the presence of silicate clay. It was also observed from wide-angle XRD analyses that the presence of nanoclays improved the gamma-form crystals and induced the formations of alpha-form crystals of the PA6, attributed to effective nucleating effects of silicate clay platelets.