5wt%B2O3-doped (Li,K,Na)NbO3 (abbreviated as LKNN-B5)-based lead-free piezoelectric ceramics were prepared via solid state synthesis. The electrical humidity sensitive properties of LKNN-B5 ceramics were examined and compared with pure LKNN ceramics. The results revealed thatB2O3 doping enhanced electrical stability of LKNN-based ceramics in relative humidity (RH) range of 33-95%. The capacitance change was suppressed from 105% down to 43% when doped with B2O3. The average absorption time was reduced from 5.5 min to 1.5 min, and desorption time decreased from 8.5 min to 2.0 min. The enhanced electrical stability of LKNN-B5 series was attributed to the dense structure induced by liquid phase sintering.