Mechanical energy harvesting from ambient vibrations is an attractive renewable source of energy for various applications. Prior research was solely based on lead-containing materials which are detrimental to the environment and health. Therefore, lead-free materials are becoming more attractive for harvesting applications. The present work is focused on the development of lead-free piezoelectric materials based on solid solution having composition (KNa)NbO 3 -xABO 3 , (where A = Li, and B = Nb; x = 0, 5, 5.5, 6, and 6.5 wt%). The solid solutions of the above ceramics were prepared by using solid-state reaction method. The X-ray diffraction spectra exhibited single phase formation and good crystallinity with LiNbO 3 addition up to x = 6.5 wt%. Dielectric studies reveal that the composition with LiNbO 3 = 6.5 wt% exhibits superior properties suitable for piezoelectric energy harvesting applications. The nanoscale piezoelectric data obtained with piezoresponse force microscopy provide a direct evidence of strong piezoelectricity with LN doping. The best piezoelectric properties are obtained for the composition K 0.5 Na 0.5 NbO 3 -6.5%LiNbO 3 .