In this work, the Ba0.95Ca0.05Ti0.92Sn0.08−x Zr x O3 (BCTSZ-x) lead-free piezoceramics were prepared by the normal sintering, and the influences of Zr content on their phase structure, microstructure, and piezoelectric activity were well investigated. The multiphase coexistence concerning of rhombohedral–orthorhombic (R–O) and orthorhombic–tetragonal (O–T) was observed in the samples with 0 ≤ x ≤ 0.02, and the R–O phase coexistence was shown in the ceramics with 0.02 < x ≤ 0.07. In addition, it was observed that the addition of optimum Zr content can improve the density of the ceramics, and all the elements are homogenously distributed in the ceramic matrix. The ceramics with x = 0.02 possess a high piezoelectric activity of ~450 pC/N due to the involvement of R–O and O–T mixed phases. As a result, the piezoelectric properties of BCTSZ-x ceramics can be operated by changing Zr content.