Structural rearrangements during the sol-gel processing of lithium niobate were investigated by FTlR and Raman spectroscopic methods. The reaction of lithium ethoxide with niobium ethoxide resulted in the formation of a bimetallic alkoxide, LiNb(OEt)6 , which could be crystallized from solution. Single crystals were comprised of helical polymeric units consisting of niobium octahedra linked by lithium in tetrahedral (distorted) coordination. Successive crystallizations from solution allowed for the enhanced purification of the alkoxide precursor. Hydrolysis of the bimetallic alkoxide resulted in the formation of an amorphous network structure, which contained niobium-oxygen octahedral units modified by lithium. Heat-treatment facilitated structural rearrangements for the niobium environment, which allowed for the formation of the lithium niobate crystal structure. Further heat-treatment above 700°C resulted in structural changes associated with lithium oxide volatility.