In this work, effect of low sintering temperature and time on the new lead-free perovskite (Ba0.7Ca0.3)TiO3-Ba(Zr0.2Ti0.8)O3 (BCZT) solid solution ceramics have been investigated. X-ray diffraction (XRD) was used to understand the phase transition of the BCZT during heating. The Curie temperature decreased nonlinearly 43 K in BCZT ceramics. Diffuse phase transitions were observed in BCZT ceramics and the Curie-Weiss exponent (CWE) was nearly 2. The dielectric permittivity versus temperature characteristics and the γ in the modified Curie-Weiss law, as a function of the dc bias field was obtained for BCZT ceramics. The fitting of parameters (Tm vs. f ) have close agreement with the data of Vogel-Fulcher’s relationship.