Laser-induced damage threshold is the main limitation for fused silica optics in high-power laser applications. The existence of various defects near the surface is the key factor for the degradation of the threshold. In this work, the photoluminescence spectra at different regions of the damaged and recovered fused silica samples are recorded to analyze the correlation between photoluminescence of surface defects and laser-induced damage threshold. The experimental data concluded the inverse proportional correlation between fluorescence and laser-induced damage threshold value. The weak photoluminescence is the guarantee of the high laser-induced damage threshold, and then the higher local Si nanocluster concentration corresponds with the higher laser-induced damage threshold value for the fused silica optics after CO2 laser treatment. The investigation reveals that photoluminescence measurement can be employed to check the quality of pristine fused silica and evaluate the tendency of the laser-induced damage threshold value. The current results are helpful for understanding the evolution of interaction from CO2 laser treatment and fused silica optics and can provide the guide of process technology for the high quality of fused silica optics.