The basic optical properties of yttrium-phosphosilicate fiber doped with bismuth (Bi) are assessed in both pristine state and that established after bombardment by a beam of high-energy electrons. The fiber has been developed and fabricated with a target to use it for laser applications in visible/near-infrared (VIS/NIR) domain. In this chapter, the main attention is paid to the dramatic changes in absorption spectra of the fiber under electron irradiation. Meanwhile, we reveal its overall resistance to irradiation in terms of emissive potential and bleaching contrast at excitation into the absorption bands of bismuth-related active centers. Besides, we report a new effect of large dose-dependent Stokes shift, experienced by the fiber's cutoff wavelength, which arises due to refractive index rise in its core area. The laws obeyed by the fiber's characteristics vs. dose are examined for possible applications in dosimetry.