A series of compounds La2MO2-xWxO9 (x = 0-2) were synthesized using a freeze-dried precursor method at relatively low temperatures (673-823 K). These materials were characterised by thermogravimetric and differential thermal analysis (TG/DTA), differential scanning calorimetric (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM) and dilatometric measurements. Oxygen stoichiometry was evaluated by coulometric titration and thermogravimetric analysis at 873-1273 K. The ionic and electronic conductivities of these materials were analysed by impedance spectroscopy and a Hebb-Wagner ion-blocking method under moderately reducing conditions. The presence of w(6+) leads to an increase of the stability range (about 10(-16) Pa for La2Mo0.5W1.5O9 at 1073 K) and prevents oxygen loss and arnorphisation. Within the stability range, the electronic conductivity increases gradually as the temperature increases and as the oxygen partial pressure reduces. This indicates that the electronic transport is mainly n-type as a result of the oxygen-content decreasing in the molybdate lattice. Further reduction of the oxygen partial pressure gave rise to the decomposition of La2Mo2-xWxO9, leading to the formation of new phases with molybdenum in lower oxidation states, which further enhances the electronic conductivity. The results of the coulometric titration and the thermogravimetric studies under a dry 5% H-2/Ar flow suggest that tungsten doped lanthanum molybdate materials can be used as electrolyte only at low temperature and under moderate reducing conditions. (c) 2005 Elsevier Ltd. All rights reserved.