The lowtemperature sintering 0.1Pb(Zn1/3Nb2/3) O3-0.1Pb(Ni1/3Nb2/3) O3-0.8Pb(Zr0.52Ti0.48) O3+x%Li2CO3(PZNPNNPZT) piezoelectric ceramics were synthesized by solidstate reaction method. The effects of Li2CO3 doping on the crystal structure, microstructure and electrical properties for the PZNPNNPZT piezoelectric ceramics were investigated. The experimental results showed that the phase structure of the PZNPNNPZT ceramic transformed from the trigonal phase to the tetragonal phase with the increase of Li2CO3, the grain size firstly increased and then decreased. The electrical properties of PZNPNNPZT ceramics can be effectively improved by doping appropriate amount of Li2CO3. When x is 0.3, the PZNPNNPZT ceramic exhibited the best comprehensive properties: the piezoelectric constant d33=530 pC/N，electromechanical coupling coefficient kp=0.55, mechanical quality factor Qm=60, Cuire temperature TC=176 ℃，relative dielectric constant εr=2 800, residual polarization intensity Pr=32.80 μC/cm2，coercivity field Ec=0.96 kV/mm.