The technique of electrospinning offers the advantage of growing nanowires in bulk quantities in comparison with traditional methods. We report optical studies of polycrystalline zinc oxide (ZnO) nanofibers (similar to 100 nm thick and 5 mu m long) deposited by electrospinning. Photoluminescence from the nanofibers shows a near-ultraviolet (near-UV) peak corresponding to near-band-edge emission and a strong broad peak in the visible region from oxygen antisite and interstitial defects. Temperature-dependent photoluminescence spectroscopy reveals that different carrier recombination mechanisms are dominant at low temperature. Our Raman spectroscopy results demonstrate that characterization of the quasimodes of longitudinal optical (LO) and transverse optical (TO) phonons present in an ensemble of polycrystalline nanofibers tilted at various angles in addition to the dominant E(2)(high) mode provides a promising technique for assessing the quality of such randomly oriented nanowires.