Large piezoelectric effect is achieved in Li-doped Ba0.85Ca0.15Ti0.90Zr0.10O3( BCTZ) ceramics by use of tuning the phase boundaries. Rhombohedral-orthorhombic ( R-O) and orthorhombic-tetragonal ( O-T) multiphase coexistence is constructed in the ceramics by changing Li contents. The high piezoelectric constant d(33) ( 493 pC/N) and large electrostrain ( dS(max)/dE(max) = 931 pm/V) have been observed in the Li-doped ( Ba, Ca)(Ti, Zr)O-3 ceramics at low sintering temperature ( 1350 degrees C/2 h). The significant enhancement in materials properties is ascribed to the multiphase region around room temperature induced by Li-doped effect.