This study reports the synthesis, structural characterization, and chemical analysis of pure NaMgF3 and CeO2-doped NaMgF3 perovskite materials. The compounds were prepared via a combined co-precipitation and solid-state reaction approach, ensuring homogeneous incorporation of cerium into the NaMgF3 lattice. X-ray diffraction XRD analysis confirmed that all samples crystallize in a single-phase orthorhombic perovskite structure (space group Pbnm) while XPS provides insights into the bonding, chemical environment, and chemical state of elements present respectively. According to XRD studies Ce incorporation inducing minor peak shifts, a slight reduction in crystallite size (from 35.7 nm to 34.7 nm), and decreased lattice strain (0.27% to 0.26%), indicating inhibition of crystal growth and defect relaxation. XPS revealed the presence of Na, Mg, and F elements and detected changes in the chemical bonding and local environments of the material’s surface after cerium (Ce) doping. The O1s, F1s, Na1s, and Mg2s core levels displayed shifts and changes peak area distributions, reflecting stabilization of lattice sites by the introduction of Ce–O and Ce–F interactions. Ce3d spectra confirmed a Ce3+/Ce4+ states ratio in NaMgF3 that significantly influences its structural properties. The specific ratio of Ce3+ to Ce4+ is critical in determining the sensitivity and signal characteristics of the material for dosimetry applications. These structural and chemical modifications are anticipated to influence electronic structure, defect states, and optical properties, enhancing potential luminescence and scintillation performance. The results demonstrate that CeO2 doping effectively tailors the structural and chemical environments of NaMgF3, establishing it as a promising candidate for advanced phosphors, scintillators, and optoelectronic applications. Therefore, future investigation will include how the Ce3+/Ce4+ ratio in NaMgF3 primarily affects its luminescence intensity and emission wavelength.