Light-guiding core/sheath fibers are fabricated from two different refractive index (RI) polymers by coaxial electrospinning. The morphology and fiber diameter are analyzed with scanning electron and fluorescence microscopies. It is found that the diameter of the core and the thickness of the sheath could be varied from 100 to 400 nm by changing the concentration of the outer solution. The incorporation of a chromophore into the inner material confirmed the uniformity of the core/sheath structure in long segments of the fibers. The boundary is clearly seen: the core diameter and the thickness of the sheath are constant along the fiber axis in fluorescence images. The ejected beam is circular and light-guided along the fiber axis as in an optical fiber.