Lead-free KNN-modified piezoceramics of the system (Li,Na,K)(Nb,Ta,Sb)O3 were prepared by conventional solid-state sintering. The X-ray diffraction patterns revealed a perovskite phase, together with some minor secondary phase, which was assigned to K3LiNb6O17, tetragonal tungsten–bronze (TTB). A structural evolution toward a pure tetragonal structure with the increasing sintering time was observed, associated with the decrease of TTB phase. A correlation between higher tetragonality and higher piezoelectric response was clearly evidenced. Contrary to the case of the LiTaO3 modified KNN, very large abnormal grains with TTB structure were not detected. As a consequence, the simultaneous modification by tantalum and antimony seems to induce during sintering a different behaviour from the one of LiTaO3 modified KNN.