The series of Dy3+ and Sm3+ activated Ca3Al10O18 phosphors with various concentrations prepared through combustion method. The XRD analysis verified that the crystalline structure is orthorhombic, matching JCPDS no. 00-001-0572, with no impurities detected. FTIR spectroscopy revealed that the bending vibrations of H2O, Ca-O, and Al-O atoms, indicating metal-oxygen stretching vibrations. The SEM image reveals micro-sized particles with irregular shapes and uneven morphology. The photoluminescence (PL) excitation spectra of Ca3Al10O18:Dy3+ phosphor showed distinct lines at 327 nm, 346 nm, 374 nm, 391 nm, 423 nm, and 452 nm, attributed due to the transitions several excited states from ground state. The most intense transition was H-6(15/2) -> P-6(7/2) (346 nm). Emission spectra exhibited strong blue (483 & 487 nm) and yellow (568 nm) luminescence peaks, with the F-6(9/2) -> H-6(15/2) blue emission being magnetic dipole-allowed transition and the F-6(9/2) -> H-6(13/2) yellow emission being induced dipole-allowed transition. The blue peaks split into two sharp peak centered at 483 nm and 487 nm. PL excitation spectra of Ca3Al10O18:Sm3+ phosphor showed peaks at 345 nm, 362 nm, 375 nm, 403 nm, and 419 nm, with the highest intensity observed at 403 nm. The emission spectra displayed intense peaks at 567 nm, 604 nm, and 657 nm, corresponding to (4)G(5/2) -> H-6(5/2), H-6(7/2), and H-6(9/2) transition of Sm3+ ion within 4f-4f electronic configuration, with the most intense peak at 604 nm. The concentration quenching observed in Dy3+ and Sm3+ activated Ca3Al10O18 phosphor at 0.7 mol%. The CIE color co-ordinates of Ca3Al10O18:Dy3+ phosphor positioned at the edge of the green-yellow and indigo-blue regions of the CIE diagram. For Ca3Al10O18:Sm3+ phosphor, the CIE co-ordinate located at the border of the yellow and red regions in the CIE diagram. These results suggest that Ca3Al10O18:RE3+ (RE3+ = Dy3+, Sm3+) phosphor is promising for use in WLEDs and display application.