Lithium-metaphosphate is an imperative matrix for the evolution of Li₄P₄O₁₂ rings and LiPO₃ chains, as well as worthy host matrix for holding photoluminescent Cu⁺, plasmonic Cu° nanoparticles and Co²⁺ color center. This has been verified by studying the mutual influence between the crystallization process and transition metal doping in 50Li₂O·50P₂O₅, 1CoO·49Li₂O·50P₂O₅ and 1CuO·49Li₂O·50P₂O₅ glasses. Samples were subjected to heat treatment, and the crystallization and molecular arrangements were examined by XRD, TEM, HRTEM, SAED and FTIR. In 50Li₂O·50P₂O₅ glass, Li₄P₄O₁₂ crystallizes with increasing the time of heat-treatment, whereas the concentrations of Q₁ and Q₂ increase. These rings are transformed into LiPO₃ in 1CoO·49Li₂O·50P₂O₅ with upturn and downturn points in concentrations of Q₂ and Q₁ at 3 and 4 h, respectively. In 1CuO·49Li₂O·50P₂O₅ glass, LiPO₃ is precipitated after 2 h, and the concentration of Q₂ increases whereas that of Q₁ exhibits a quite small decrease with the time of heat-treatment. Furthermore, 1CuO·49Li₂O·50P₂O₅ exhibits a higher crystallization rate than 1CoO·49Li₂O·50P₂O₅, which is attributed to a higher rate of cluster formation, as revealed by SEM and TEM micrographs. This enhancement is attributed to the coordination of Co ions by 4 and/or 6 oxygen atoms, while Cu ions have a redox state of 0 or +1, as deduced from UV–Vis spectroscopy. Also, the existed intrinsic defects in 50Li₂O·50P₂O₅ are reduced by the addition of CoO. In contrast, photoluminescent Cu⁺ ions contribute to such defects, and are reduced into Cu° during the crystallization process.