As an lead-free piezoelectric ceramic of (1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3(here after (1-x)BZT-xBCT) has been investigated for functional devices applications. To employ as piezoelectric functional devices applications, lead-free materials with high piezoelectric charge coefficient and voltage coefficient can be indispensable for industrial applications. Piezoelectric ceramic specimens tend to shrink their size in the sintering process without melting. We focused on this phenomenon as a unique characteristic of piezoelectric ceramic materials and derived activation energy from this phenomenon using Arrhenius equation. Then associate this activation energy with piezoelectric and crystalline properties varied by sintering temperature and chemical stoichiometric composition. Piezoelectric properties can be changed depending on the sintering temperature and process conditions. (1-x)BZT-xBCT ceramics showed the highest piezoelectric coefficient of 470 pC/N. Crystalline properties and piezoelectric properties can be influenced by the sintering temperature and holding times. In this research, sintering temperature dependent structural and dielectric properties were investigated. Sintering temperature dependent shrinkage rate and activation energy were estimated and calculated for the various sintering process. In this research, two different activation energies for the shrinkage process were estimated