The effects on microstructure, piezoelectric properties, the aging rate, and the non-deliquescence of 95NKN-5LiSbO3 lead-free piezoceramics (KNN-LS) have been investigated. The experiment results show that a large difference caused by doping CeO2 in the sintering temperature, the mass loss, piezoelectric properties, microstructure appeared. The detailed analysis for the physical mechanism causing these differences is conducted. Samples with high piezoelectric constant (255pC/N), high relative density (98.1%), low aging rate and strong performance against deliquescence are prepared, which indicate that this ceramics is a promising and practical lead-free piezoelectric ceramics.