In this study, the structural and spectroscopic properties of orthorhombic PbNb2O6 doped with different concentrations of Eu3+ were studied. Interestingly, XRD analysis of undoped PbNb2O6 showed rhombohedral phase while Eu3+ doped structures exhibited an orthorhombic phase at 1250 °C. This difference was also observed in the morphology and composition of grains by SEM-EDS analysis. PL and RL emissions occurred between 550 and 850 nm owing to the 4f–4f transitions of Eu3+. The Judd-Ofelt theory was applied to the experimental data for determination of the Judd-Ofelt parameters (Ω2, Ω4), radiative transition rates (Ar) and radiative lifetimes (τr). TL glow curves were monitored by the peaks of 98 and 250 °C while emission increased up to 6 mol%. TL emission of 6 mol% phosphor depending on X-ray irradiation dose exhibited the highest intensity for 1200 Gy and appeared new peaks. Moreover, the TL emission of phosphor showed a linear relation with X-ray irradiation. The deconvolution peaks of 1200 Gy irradiated samples were determined by the CGCD method. Kinetic data of first peak (98 °C) depending on the dose increase were calculated by the PS method.