Abstract: Li₂CO₃ was added while a series of CaSiO₃:Pb²⁺,Mn²⁺ phosphor were synthesized by Sol-Gel method,and the influence of Li⁺ doped on the crystal structure and luminescent properties of CaSiO₃:Pb²⁺,Mn²⁺ were investigated via PL,DTA-TG,XRD and SEM.The results show that when the sample was calcinated at 900℃ and the mass fraction of Li⁺ was no more than 0.25%,no shift in the emission band was found.When the mass fraction of Li⁺ was 0.15%,the emission intensity of the sample was most prominent,and the β-CaSiO₃ crystalline phase was observed.When the mass fraction of Li⁺ was more than 0.25%,blue shift in the emission band was observed.When the mass fraction of Li⁺ was 0.65%,the emission intensity of the sample was enhanced 3.5 times compared to that of the sample without Li⁺doped,and the emission band shifted from 650 nm to around 615 nm,and a new sort of material,Li₂Ca₃Si₆O₁₆ was observed.It was also found that the synthesis temperature was decreased as Li⁺ was added.The best calcination temperature for the sample without Li⁺ doped was 1 200℃;when the mass fractions of Li⁺ were 0.15% and 0.65%,the best calcination temperatures were 1 100℃ and 900℃ respectively.SEM also showed that with Li⁺ added,the shape of the products gradually turned irregular from 3-dimensional network structure,and the size of the phosphor particles became smaller.