Ceramic powders of Na_1−xLi_xNbO₃ (LNN) have been synthesized by an aqueous sol–gel route. These solid solutions were prepared from Na–Li–Nb precursor gel. The precursor was synthesized from Na–EDTA, Li–EDTA and Nb–citrate complexes and they acted as the source of Na, Li and Nb, respectively. Citric acid and ethylenediaminetetraacetic acid (EDTA) were used as the chelating agents for Na, Li and Nb. The precursor gel was calcinated on a muffle furnace at 750 ℃ for one hour and this provided the ceramic structures. Composites of LNN–biopolymers were prepared by the encapsulation of the ceramic structures into the biopolymeric scaffolds. The ceramic structures and composites were characterized by FTIR, NMR, TG and SEM analysis.