In this work, were synthesized (Pb0.91La0.09)(Zr0.65Ti0.35)0.9775O3 ceramic materials with different concentrations of praseodymium (0, 0.1, 0.3, 0.5, 1 wt.%) via gel-combustion route and sintered by the hot uniaxial pressing method. Measurements were conducted on the obtained ceramics using X-ray powder diffraction (XRD), scanning electron microscope (SEM), EDS analysis, and examination of dielectric and ferroelectric optical properties. Results give us a detailed account of the influences of the praseodymium ions on the structural, microstructural, and dielectric properties. 3D fluorescence maps and excitation and emission spectra measurements show how a small admixture changes the ferroelectric relaxor behavior to an optically active ferroelectric luminophore.