A new phase boundary with rhombohedral–orthorhombic and orthorhombic–tetragonal phase boundaries is designed in (K 0.48 Na 0.52 )NbO 3 by adding Bi 0.5 (Na 0.7 K 0.2 Li 0.1 ) 0.5 ZrO 3 (BNKLZ), where Zr 4+ and (BNKL) 2+ are respectively used to improve the temperature of a rhombohedral phase and to decrease the temperature of an orthorhombic–tetragonal phase coexistence. These ceramics endure several continuous phase transitions with increasing BNKLZ content, i.e., an orthorhombic phase (0≤x<0.03), orthorhombic–tetragonal phases (x=0.03), orthorhombic–tetragonal and rhombohedral–orthorhombic (O–T and R–O) phase existence (0.03<x≤0.05), a rhombohedral phase (0.05<x≤0.07). The ceramics with O–T and R–O have a better piezoelectric behavior as compared with other phases because of more polarization states, enhanced ε r and P r , and a dense microstructure. Moreover, piezoelectric properties could be further optimized by modifying their sintering and poling temperatures. As a result, the construction of O–T and R–O phase coexistence benefits the improvement of piezoelectric properties in KNN-based ceramics.