Abstract <p>Synthesis of (MgCa)₂Bi₄Ti₅O₂₀ powder ceramics activated with (0.2 mol %) Eu³⁺, Tb³⁺, Sm³⁺, and Dy³⁺ ions was achieved via solid-state reaction method and aimed to investigate the optical properties comparatively. Notably, the emission spectra revealed distinct characteristics for each dopant. Eu³⁺ shows prominent emission band at 615 nm on excitation at 393 nm, while an excitation at 376 nm in Tb³⁺ exhibited green emission at 542 nm. Similarly, Sm³⁺ displayed intense reddish-orange emission at 599 nm with an excited wavelength at 405 nm, and Dy³⁺ emitted yellow light at 583 nm with an excitation wavelength of 426&#xa0;nm. These findings emphasized significant luminescent performance of the rare earth ion-doped (MgCa)₂Bi₄Ti₅O₂₀ ceramic host. Among these rare earth ions, Sm³⁺:(MgCa)₂Bi₄Ti₅O₂₀ ceramic powder has shown strong luminescence intensity with its characteristics and energy band structure. Furthermore, structural and morphological analyses have been carried out by using XRD, SEM, and EDAX techniques, providing comprehensive insights into the characteristics of the ceramic powders.</p>