A facile compounding process, which combined nanocomposite process with electrospinning for preparing novel polyamide6/organic modified montmorillonite (PA6/O-MMT) composite nanofibers, is reported. In this compounding process, the O-MMT slurry was blended into the formic acid solution of PA6 at moderate temperatures, where the nanosized O-MMT particles were first dispersed in N,N-dimethyl formamide solvent homogeneously via ultrasonic mixing. Subsequently the solution via electrospinning formed nanofibers, which were collected onto aluminum foil. The O-MMT platelets were detected to be exfoliated at nanosize level and dispersed homogeneously along the axis of the nanofibers using an electron transmission microscope. Scanning electron microscope and atomic force microscope were used to analysis the size and surface morphology of polyamide6/O-MMT composite nanofibers. The addition of O-MMT reduced the surface tension and viscosity of the solution, leading to the decrease in the diameter of nanofiber and the formation of rough and ridge-shape trails on the nanofiber surface. The behavior of the dynamic water adsorption of composite nanofibers was also investigated and discussed in this article.