The (1 - x)PbZrO3-xPb(Yb1/2Nb1/2)O-3 (PZ-PYbN) ceramics, with the compositions, x = 0.00-0.50, were prepared by the wolframite precursor method. The crystal structure and electrical and thermal properties of PbZrO3 ceramic were investigated as a function of the composition, x, using X-ray diffraction, dielectric spectroscopy, hysteresis measurement and differential scanning calorimetry techniques. The results indicated that the solid solution, PZ-PYbN, changed from orthorhombic to rhombohedral symmetry when the amount of PYbN increased. The pyrochlore phase identified as Yb/Nb mixed compound was observed at the composition, x >= 0.2. For the compositions, x = 0.00-0.10, ceramics showed a sharp phase transition from AFE to PE. Furthermore, the intermediate FE phase was absent from the PZ-PYbN system.