Phase composition, morphology and surface properties of nylon-6 nanofibers prepared by Nanospider technology have been studied for dependence on spinning distance using a combination of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electrokinetic analysis, and scanning electron and transmission electron microscopy (SEM, TEM). The effect of the electric field strength on the nanofiber phase composition was investigated via the variable distance of the electrodes. Quantitative XRD phase analysis revealed the dependence of the phase composition on the electrode distance, which in the case of roller electrospinning, differs from that by melt spinning. A combination of XRD, XPS, and TEM suggested a core-shell structure model of the nanofibers. The XPS and electrokinetic analysis revealed the difference in surface chemistry and zeta potential at the face and reverse side of the nanofiber textile adjacent to a polypropylene (PP) antistatic spunbond, which may be important in subsequent chemical modification of nanofiber textiles and in its use for tissue engineering.