Barium and strontium zirconates and niobates were prepared by means of an economic and ecologic aqueous solution-gel route with high compositional flexibility. The synthesis of precursor solutions and gels, and thermal analysis of the gels are presented. The crystallization of the different oxides was studied in situ using high-temperature X-ray diffraction measurements (HT-XRD). Zirconate crystallization was observed between 600 degrees C and 700 degrees C. Small amounts of Ba(II)- and Sr(II)-carbonate crystallized before the oxide did, and decomposed between 700 degrees C and 800 degrees C. More sensitive Fourier transform infrared spectra, showed that very small traces of carbonate remain at 900 degrees C. The crystallization behavior of strontium niobates was strongly dependent on the Sr:Nb ratios, as observed in HT-XRD. Phase pure SrNb(2)O(6) was obtained at low temperature (600 degrees C). Sr(2)Nb(2)O(7) and Sr(5)Nb(4)O(15) were formed at 900 degrees C from an intermediate phase, with a minor secondary phase. Nb(2)Sr(4)O(9) crystallized at 600 degrees C, but transformed to a mixture of phases at high temperature (1000 degrees C). By off-line furnace annealing, phase pure strontium niobates of all four compositions were obtained. The presented work demonstrates the high compositional flexibility of the aqueous solution-gel route, allowing fast synthesis of different multimetal oxides with high purity. (C) 2008 Elsevier Ltd. All rights reserved.