The effect of Pr3+ addition on structural, electrical, and optical properties of Ba1-xPr2x/3Ti0.925(Yb0.5Nb0.5)0.075O3 (0.3% ≤ x ≤ 1%) ceramics was investigated. X-ray studies have allowed the identification of a continuous solid solution with P4mm-tetragonal symmetry of all prepared samples. Incorporation of Pr3+ was found to improve ferroelectric and piezoelectric properties with an optimum at the critical concentration of 0.005. Photoluminescence properties revealed that the introduction of Pr3+ ions gives rise to the green and red photoemissions and permitted to shed more light on the created structural disorder and shallow defects. This effect was confirmed by Raman spectroscopy investigation. The presence of Pr element in such materials may have significant technological promise in novel multifunctional devices. © 2016 Elsevier B.V.