Nanomaterials, materials with particle dimensions less than 100 nm, show a range of unusual properties when compared with their bulk counterparts. Atomic transport is one of these properties and nanomaterials have been reported as having exceptionally high diffusion coefficients. In the case of ionic materials the atomic transport is important in a number of technological applications where they are used as solid electrolytes, for example in sensors, batteries and fuel cells. Hence ionic nanomaterials often referred to as nanoionics, can offer the means of producing electrolytes with improved performance. This contribution will examine the mechanisms of atomic transport in nanoionics in two model materials, zirconia and lithium niobate. Since an understanding of these mechanisms is dependent on knowledge of the microstructure of the materials consideration will also be given to the structural characterisation of the materials, with a focus on X-ray absorption spectroscopy. The use of this technique to characterise mesoporous a-Fe2O3 is also discussed. (c) 2006 Elsevier B.V. All rights reserved.