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Phosphate glass-clad optical fibers containing selenium (Se) semiconductor core were fabricated using a molten core method. The cores were found to be amorphous as evidenced by X-ray diffraction and corroborated by Micro-Raman spectrum. Elemental analysis across the core/clad interface suggests that there is some diffusion of about 3 wt % oxygen in the core region. Phosphate glass-clad crystalline selenium core optical fibers were obtained by a postdrawing annealing process. A two-cm-long crystalline selenium semiconductor core optical fibers, electrically contacted to external circuitry through the fiber end facets, exhibit a three times change in conductivity between dark and illuminated states. Such crystalline selenium semiconductor core optical fibers have promising utility in optical switch and photoconductivity of optical fiber array.