(1−x)(K 0.5 Na 0.5 )NbO 3 –xLiNbO 3 ((1−x)KNN–xLN) nanoparticles with the mean particle size about 20–30nm have been prepared by an economical sol–gel routes using Nb 2 O 5 as Nb source. Due to the high sintering ability of nano-particles, fine-grained KNN–LN lead-free ceramics have been densified at the temperature below 1000°C. X-ray diffraction analysis indicated that the phase structure of the ceramics changed from orthorhombic to tetragonal at x=0.08–0.10. When the x reached 0.10 and above, the perovskite structure could not be maintained and the impurity phases of K 3 Li 2 Nb 5 O 15 and LiNbO 3 appeared, indicating that x=0.10 is near the solubility limit. Optimized parameters, such as d 33 =170 pC/N and k p =0.40, were achieved in 0.90KNN–0.10LN systems. Due to the merits of fine-grained structure and low sintering temperatures, it will be helpful to the application of KNN–LN materials for lead-free multilayer piezoelectric actuator.