Micrometer and submicrometer diameter of polystyrene (PS) fibers were electrospun from various dimethyl formamide (DMF) solutions at different weight fractions under 35% relative humidity. Increasing polymer fraction in the solution results in a gradual morphological transition from beads-with-incipient to bead-free fibers and also increases the diameter. The formation of uniform glassy skin presumably due to radial capillary flow within the liquid jet was confirmed by scanning electron microscope. The thickness of the skin varies with the weight fraction of PS; therefore, it was normalized with respect to average fiber diameter (AFD). The skin gets thinner as the weight fraction of PS increases. In addition, the fibers exhibit highly porous internal structure and smooth surface along with slight porosity. The development of porosity is attributed to liquid-liquid phase separation of water molecules in atmospheric moisture and DMF.