Electrospinning process uses high voltage electric field to produce fibers in submicron to nanometer levels. The charged fibers move towards the oppositely charged collector electrode and arrange in three-dimensional patterns as nanofiber webs. The first known self assembling phenomenon in polyurethane electrospun fibers has been reported here. Electrospun Polyurethane nanofibers self-assembled into unique honeycomb patterns on the collector surface. Scanning electron micrographs clearly revealed the honeycomb meshes with wall like boundaries formed by the self-assembled fibers. This novel observation opens up new and improved opportunities for electrospun fibers that could find advanced applications in the areas of nano drug delivery devices, protective clothing, filters and tissue scaffolds. Electrospinning technique has also been used to fabricate metal oxides dispersed on nanofiber matrix. The capability of this technique has been demonstrated by two metal oxides (Magnesium oxide and Titanium dioxide) impregnated separately on the polyethylene oxide nanofibers. The nanofibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Electron dispersion spectroscopy (EDS) and X-ray diffraction (XRD) technique. Beside that the adsorption capabilities of both magnesium oxide and titanium dioxide nanofibers were studied. Since Titanium dioxide is known to be a UV radiation blocker, the ultraviolet protection factor for Titanium dioxide nanofiber has been measured.