Ultraviolet absorption and laser excitation spectroscopy (LES) measurements are presented for rare-earth-doped optical fibers produced from both glassy and crystalline preforms. Absorption spectra are obtained via broad-spectrum UV LEDs emitting in the 250nm region. LES measurements are obtained utilizing a tunable UV laser source. The tunable laser employed is a frequency-doubled titanium:sapphire laser-pumped optical parametric amplifier (OPA) operating down to a minimum wavelength of about 225nm. Our results indicate a roughly linear relationship between the concentration of oxygen deficiency centers (ODC) and rare-earth content, regardless of the preform type, and the slope of the line is found to vary significantly with the rare earth. Additionally, LES measurements are used to elucidate the energy transfer mechanism from pumping in the UV to emission by the rare-earth. In all cases the fibers are Al codoped and those produced from glassy preforms are manufactured via standard methods. Fibers produced from crystalline preforms start with a pure silica-sleeved rare-earth doped YAG crystal rod that becomes glassy (amorphous) post-draw.