With close attention being paid to environmental issues and more legislation coming into force to limit the application of Pb-based materials, accelerating research on lead-free piezoelectric ceramics has become increasingly requisite and urgent. Herein, we have devised and synthesized (1-x)(K0.5Na0.5)0.98Ag0.02(Nb0.96Sb0.04)O3-x(Bi0.5Na0.5)ZrO3 [abbreviated as (1-x)KNANS-xBNZ, x = 0.01, 0.02, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06] Pb-free ceramics. Phase transition, microstructure, electrical properties, and temperature stability of the ceramics have been comprehensively investigated. The findings illustrate that optimizing BNZ content can give rise to a rhombohedral-tetragonal (R-T) phase boundary when x = 0.04, 0.045, 0.05. The specimens with x = 0.04 show improved piezoelectric properties (d33 ~ 440 pC/N, kp ~ 53%, TC ~ 250 °C, d33* ~ 553 pm/V) and good temperature stability. The overall performance is excellent and indicates that (1-x)KNANS-xBNZ ceramics have great potential for replacing their lead-based counterparts.