A series of multi-component fluoride-containing phosphate-based glasses prepared in a reducing atmosphere showed improved resistance to high-energy ultraviolet (UV) laser-induced damage and strong laser-induced fluorescence (LIF) within the glass bulk. The UV optical absorption, photoluminescence, and fluorescence decay properties of these glasses were investigated to explore the defect-related LIF mechanism and its underlying effect on the glasses? laser-induced damage threshold (LIDT). Seven laser wavelengths ranging from 253 nm to 532 nm were used to excite the LIF, and two characteristic fluorescence bands peaking at approximately 414 nm and 780?800 nm occurred in all three types of glasses. The LIF band at 414 nm was attributed to PO3-EC defects in the second harmonic frequency (2?) absorptive glass and third harmonic frequency (3?) transparent glass, but Fe2+ ions in the fundamental frequency (1?) absorptive glass. A later fluorescence band at 780?800 nm occurred due to POHC defects in the 2? absorptive and 3? transparent glasses and Fe3+ ions in the 1? absorptive glass. A detailed study on the dynamic decay processes of two additional dominant fluorescence peaks at 450 nm and 780 nm under 266 nm excitation revealed the potential effect of LIF on LIDT improvement. The relatively longer LIF lifetime, higher LIF intensity, and larger LIF peak area corresponded with and contributed to a higher LIDT, especially in the 3? transparent glass with a low UV absorption coefficient. This study provides strong evidence for the prior hypothesis between strong LIF and LIDT.