The praseodymium Pr3+ doped BaTi0.9(Yb0.5Nb0.5)(0.1)O-3 (BTYN01) ceramic, under low concentration (0.1%), was prepared by a conventional ceramic fabrication technique and its phase structure, microstructure, dielectric, vibrational and photoluminescence (PL) properties was studied. Both X-ray diffraction (XRD) and Raman studies confirmed the incorporation of Pr3+ into A-site lattice of BTYN01. The structure of Ba0.9985Pr0.001 square Ti-0.0005(0.9)(Yb0.5Nb0.5)(0.1)O-3 (BTYN01-Pr) shows the coexistence of Pm (3) over barm-cubic symmetry (similar to 10%) and P4mm-tetragonal symmetry (similar to 90%) at room temperature. The dielectric study reveals that the maximum of the dielectric constant of BTYN01-Pr occurred at 283 K. The incorporation of Pr3+ has not change significantly the temperature of transition of BTYN01, but makes its transition peak more broadened. Contrary to BTYN01, doping with the Pr3+ allowed us to accommodate a PL response with a strong single red emission localized at about 648 nm. The temperature dependence on up-conversion emissions of BTYN01-Pr ceramic, obeying an Arrhenius law with a weak energy activation (E-a = 0.04 eV), indicates that the mechanism of PL emission is probably related to the vibrational property of the lattice. The Pr3+ doped BTYN01 red emission material with dielectric properties might have important technological promise in novel multifunctional devices.