CaSiO 3 :Eu 0.08 3+ Bi 0.002 3+ and Sr 2 SiO 4 :Eu 0.08 3+ Bi 0.002 3+ were synthesized by the sol–gel method, and their structure and luminescence characteristics were investigated. The XRD results showed that the symmetry of Sr 2 SiO 4 :Eu 0.08 3+ Bi 0.002 3+ structure, which is similar to the non-close-packing orthogonal structure of K 2 SiO 4 is higher than that of CaSiO 3 :Eu 0.08 3+ Bi 0.002 3+ perovskite structure belonging to the monoclinic system. From the excitation spectra of CaSiO 3 :Eu 0.08 3+ Bi 0.002 3+ and Sr 2 SiO 4 :Eu 0.08 3+ Bi 0.002 3+ , it can be seen that the main peaks located at 267nm, 383nm, 395nm, 437nm, 457nm and 359nm, which correspond to the charge transfer band of Eu 3+ –O 2− , absorption transition of 7 F 0.1 – 5 G J , 7 F 0.1 – 5 L 6 , 7 F 1 – 5 D 3 and 7 F 0.1 – 5 D 2 of Eu 3+ ions and 3 P 1 – 1 S 0 of Bi 3+ ions, respectively. When the CaSiO 3 :Eu 0.08 3+ Bi 0.002 3+ samples were excited with wavelength of 359nm, the emission intensity of electronic dipole transition at 609nm originated from 5 D 0 – 7 F 2 of Eu 3+ ions was stronger than magnetic dipole transition at 587nm originated from 5 D 0 – 7 F 1 of Eu 3+ ions mainly due to the lower symmetry and the distortion of the structure. However, the opposite situation appeared in the emission spectrum of Sr 2 SiO 4 :Eu 0.08 3+ Bi 0.002 3+ . In addition, the intensity comparison of each emission peaks between the emission spectra of CaSiO 3 :Eu 0.08 3+ Bi 0.002 3+ and Sr 2 SiO 4 :Eu 0.08 3+ Bi 0.002 3+ showed that the energy transfer efficiency between Bi 3+ ions and Eu 3+ ions in Sr 2 SiO 4 :Eu 0.08 3+ Bi 0.002 3+ is apparently higher than that in CaSiO 3 :Eu 0.08 3+ Bi 0.002 3+ .