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The Cu-doped phosphosilicate glasses were prepared with conventional melt-quenching method and different Cu species were identified in the glasses as melt.At low concentrations of cooper(0.02mol%,0.04mol%,0.1mol%),Cu nanoparticles(NPs)could be formed in the glass host without any reducing agent or any reducing atmosphere,while divalent Cu2+ ions appeared at concentrations of cooper(0.2mol%,0.4mol%,0.6mol%).Different Cu species could be identified by the absorption band of the glasses.The broad band from 500 nm to 1200 nm could be related with d-d transition ofCu2+.The intense band at~590 nm could be assigned to the surface plasmonic resonance of Cu NPs.The band at~310 nm was caused by the charge transfer of the O2-→Cu2+.The band at~280nm was owing to the 1Ag→1Egtransition for the Cu+ ions.It revealed the conversion of Cu0(→←)Cu+(→←)Cu2+ in the glasses.The microstructural mechanism of the Cu0(→←)Cu+(→←)Cu2+ conversion was proposed and the effect of Cu-concentration on photoluminescence properties of the glasses was also further discussed.