Ba0.95Ca0.05Ti1-xZrxO3 (BCTZO) ceramics were prepared by a solid state reaction method. The samples were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray absorption near edge structure (XANES). The ceramics exhibit a pure perovskite structure. The average grain size gradually decreases with increasing Zr concentration. XANES results indicate that the intensities of pre-edge peaks dropped with increasing Zr concentration. The BCTZO ceramic of x = 0.05 has the optimum electrical properties with the maximum dielectric constant (ε'm), remanent polarization (2Pr), coercive electric field (2Ec) and piezoelectric charge constant (d33) of 7,244, 12.54 (μC/cm2), 5.29 (kV/cm) and 288 (pC/N), respectively.