A series of phosphors such as Ca2GdZr2Al3O12…Mn 4+ are synthesized by high-temperature solid-state reaction, and their phase structures and luminescence properties are characterized with X-ray powder diffractometer (XRD), fluorescence spectrophotometer and UV-visible spectrophotometer. The matrix structure indicates that Zr 4+ in the [ZrO6] octahedron can be substituted by Mn 4+. The XRD patterns and the luminescence intensity of phosphors synthesized at different temperatures indicate that 1500 °C is the suitable synthesis temperature. When the doping concentration (mole fraction) of Mn 4+ is 0.0050, the luminescence intensity is the strongest. When the detection wavelength is 703 nm, the excitation wavelength shifts from 343 nm to 374 nm as the increase of the Mn 4+ doping concentration. Using the spectral data to calculate the crystal field parameters Dq and Racah parameters (B and C), the results indicate that Mn 4+ is in a strong field. At the same time, codoping Bi 3+and Mn 4+ can enhance the luminescence of Mn 4+. The fluorescence lifetime test shows that the fluorescence lifetimes of codoped phosphors is longer than that of single-doped Mn 4+, and there is energy transfer of Bi 3+→Mn 4+.