Ceramic pellets of (Ba1-kCak)(Zr1-zTiz)O3, (k = 0.140-0.160, z = 0.9) were prepared via solid-state reaction technique followed by double sintering. The impedance measurements were carried out at different temperatures and frequencies (12-1000 kHz). The NTCR nature exhibits the semiconducting behavior of the prepared BCZT ceramics in the measured temperature range. The temperature also has a considerable impact on the relaxing process. The characteristics of Nyquist plots show that bulk and grain boundary effects exist in BCZT ceramics. The bulk conductivity indicates an Arrhenius-type thermally activated process. The observed impedance spectra, relaxation behavior, and AC conductivity of the prepared compositions of BCZT ceramics will extend the possibilities for using this compound in various optoelectronic applications.