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In this work, we revealed the possible mechanisms of the photodarkening in Pr3+ ions singly doped and Pr3+/Ce3+ co‐doped silicate glasses and fibers induced by X‐ray and 488‐nm laser radiations and studied the role of Ce3+ in increasing radiation resistance in Pr3+‐doped silicate glasses and fibers. The absorption, emission, electron paramagnetic resonance (EPR), radiation induced attenuation spectra, and X‐ray photoelectron spectroscopy (XPS) of Pr3+ singly doped and Pr3+/Ce3+ co‐doped silicate glasses before and after X‐ray radiation were measured and analyzed. The fluorescence intensity and photoinduced attenuation of Pr3+ singly doped and Pr3+/Ce3+ co‐doped silicate fibers at visible wavelengths pumped by 488‐nm laser were measured and analyzed. The influence of Ce3+ ions co‐doping on the spectroscopic properties of Pr3+ ions as well as the radiation‐induced defects in silicate glasses was studied. Results demonstrate that both X‐ray and 488‐nm laser radiations will induce photodamage in Pr3+ ions‐doped silicate glasses and fibers. Co‐doping Ce3+ (by up to 1 mol%) is efficient to suppress the darkening induced by both X‐ray and 488‐nm laser radiations without influence on the luminescence behavior of Pr3+ ions in silicate glasses and fibers. Our studies demonstrate the promising potential of Pr3+/Ce3+ co‐doped silicate glasses for visible lasing applications. [ABSTRACT FROM AUTHOR]

• The photodarkening mechanism of Tb3+/Al3+ co-doped silica glasses was revealed. • Influence of Al3+ on optical properties of Tb3+ in silica glasses was studied. • X-ray radiation induced defects in Tb3+/Al3+ co-doped silica glasses were studied. • Valence changes behavior of Tb3+ ions and defects in silica glasses were revealed. In this work, Tb3+/Al3+ co-doped and Al3+ single doped silica glasses are taken as the research objects, and X-ray is used as the simulated light source to study the photodarkening mechanism. Detailed optical properties of the glasses before and after X-ray irradiation and the results of electron paramagnetic resonance (EPR) indicate that the photodarkening effect is attributed to the valence changes of Tb3+ ions and the energy transfer between Tb3+ ions and related defects. In addition, this work revealed the relationship between valence changes behavior of Tb3+ ions and various defects in glass matrix materials, deepening the understanding of the photodarkening mechanism in Tb3+ doped oxide glass. We envisage that our finding provides a depth-theoretical support for the synthesis of Tb3+-doped oxide matrix glass fibers with excellent optical and anti-photodarkening performance. [ABSTRACT FROM AUTHOR]