The process of electrospinning uses a high-voltage source to produce an electrostatically driven jet of polymer solution that thins and elongates as it is driven toward an electrically grounded target. The fiber diameters which result from this process are on the order of nanometers to micrometers and can have large surface area to weight ratios. These high surface area fibers offer significant advantages for applications including nanocomposites, filtration media, barrier, and biomedical applications. Consequently, there are many areas of active scientific research currently focused on electrospun polymeric fibers. Because of the major commercial role played by polyolefins, there is significant interest in electrospinning these particular polymers. Polyolefins are not particularly amenable to electrospinning due to solubility and conductivity issues. Linear low-density polyethylene (LLDPE) microfibers were electrospun from solutions of p-xylene. Polyethylene readily crystallizes from solution, which requires the solution to be maintained at an elevated temperature throughout the electrospinning process. The polyethylene fibers resulting from the electrospinning process were characterized in terms of surface morphology, compositional and conformational changes, and crystalline structure using FTIR, Raman spectroscopy, FESEM, EDAX, X-ray diffraction, and DSC.