The La(2-x)A(x)Mo(2)O(9-delta)(A = Ca2+, Sr2+, Ba2+ and K+) series has been synthesised as nanocrystalline materials via a modification of the freeze-drying method. The resulting materials have been characterised by X-ray diffraction (XRD), thermal analysis (TG/DTA, DSC), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The high-temperature P-polymorph is stabilised for dopant content x > 0.01. The nanocrystalline powders were used to obtain dense ceramic materials with optimised microstructure and relative density > 95%. The overall conductivity determined by impedance spectroscopy depends on both the ionic radius and dopant content. The conductivity decreases slightly as the dopant content increases in addition a maximum conductivity value was found for Sr2+ substitution, which show an ionic radii slightly higher than La3+ (e.g. 0.08 S cm(-1) for La2Mo2O9 and 0.06 S cm(-1) for La1.9Sr0.1Mo2O9-delta at 973 K). The creation of extrinsic vacancies upon substitution results in a wider stability range under reducing conditions and prevents amorphisation, although the stability is not enhanced significantly when compared to samples with higher tungsten content. These materials present high thermal expansion coefficients in the range of (13-16) x 10(-6) K-1 between room temperature and 753 K and (18-20) x 10(-6) K-1 above 823 K. The ionic transport numbers determined by a modified emf method remain above 0.98 under an oxygen partial pressure gradient of O-2/air and decreases substantially under wet 5% H-2-Ar/air when approaching to the degradation temperature above 973 K due to an increase of the electronic contribution to the overall conductivity. (c) 2007 Elsevier Ltd. All rights reserved.