PA66/organoclay nanocomposite fibers have been prepared by electrospinning melt pre-compounded PA66/organoclay nanocomposites in hexafluoroisopropanol. The influences of solution concentration and organoclay loading on the morphology of the electrospun fibers have been studied by scanning electron microscopy. The dispersion of organoclay in PA66 fibers has been characterized by X-ray diffraction and transmission electron microscopy, showing that partial exfoliation and partial intercalation state of organoclay can be obtained when organoclay content is as high as 7.5 wt%. Organoclay platelets are oriented parallel to the axial direction of the fibers. The influences of organoclay loading on the crystallization behavior of PA66 and mechanical properties of the electrospun fiber mats have been investigated. Only a crystals of PA66 were observed in the fibers regardless of organoclay loading. Organoclay shows strong reinforcing effect, leading to a significant increase in tensile modulus.