Ba0.85Ca0.15Ti0.9Zr0.1O3 (BCTZ) ceramics, one of the lead-free pizoelectric materials, were focused due to the environmental concern against lead. A modified BCTZ powder sol-gel fabrication process was experimentally introduced with the addition of glycerol, in order to provide an effective approach to optimize the piezoelectric response of BCTZ ceramics. The results showed that the piezoelectric properties enhanced in terms of the piezoelectric coefficient of d33, 510 pC/N and the electromechanical coupling coefficient of kp, 0.501. The enhancement in electrical properties, such as dielectric, ferroelectric and piezoelectric, could be related to the homogenous microstructure and larger grain size of BCTZ ceramic powders after the introduction of glycerol during the modified sol-gel strategy.