Ceramic pellets of (Ba1-xCax)(Zr1-yTiy)O3, (x = 0.140 to 0.160, y = 0.9), were prepared via solid- state reaction method followed by double sintering. Dielectric properties (ε, tan δ, and σ) of the prepared compositions were measured, in the temperature range from room temperature (RT) to 450°C, at various frequencies (12- 1000 kHz). The dielectric measurements show a single phase transition, at around 100°C, for the prepared (Ba1-xCax)(Zr1-yTiy)O3 (BCZT) compositions, in the measured temperature range. The structural variation was studied using high temperature X- ray diffraction (HT- XRD) measurements of the compositions with x = 0.150 and 0.155. The HT- XRD results were found consistent with the dielectric measurements, showing structural anomaly at around 100°C; showing tetragonal phase, between RT and around 100°C; and cubic phase, above 100°C, in the measured temperature range.