Polystyrene/gold nanoparticle (PS/AuNP) composite fibers were fabricated using an electrospinning technique. Transmission electron microscopy (TEM) showed that the diameters of the naphthalenethiol-capped gold nanoparticles (prior to incorporation into the PS fibers) ranged from 2 to 5 nm. UV-vis spectroscopy revealed the surface plasmon peaks of the gold nanoparticles centered at approximately 512 nm, indicating that nano-sized Au particles are well-dispersed in solution. This was consistent with the TEM observations. The electrospun nanofibers of PS/AuNP composites were approximately 60-3,000 nm in diameter. The surface morphology of the PS/AuNP composite and the dispersability of the Au nanoparticles inside of PS after electrospinning process were investigated by SEM and TEM. The thermal behavior of the pure PS and PS/AuNP nanocomposites and fibers were examined by DSC.