A series of polyaniline-Fuller's Earth (PANI-FE) nanocomposites were prepared by the successive intercalation of anilinium ions followed by polymerisation within the interlayer spaces of Fuller's Earth (a type of calcium montmorillonite). The first member in the series is prepared by exchanging the calcium ions in Fuller's Earth for ammonium ions and subsequently for anilinium ions and polymerising the latter using an externally introduced oxidant. The emeraldine salt form of polyaniline formed is then neutralised with ammonium hydroxide and more anilinium ions are exchanged for ammonium ions and polymerised to get the second member. In this manner, by making use the unique chemistry of clay and polyniline, four members of PANI-FE are prepared. In the last member, the negative layer charges of Fuller's Earth is completely neutralised by the positive charges of the polymer. The extent of polymer loading in each stage, the effect polymer has on the host structure and the electronic and ionic components of the conductivities of the new PANI-FE nanocomposites are investigated. The Fe(III) sites in FE are capable of spontaneously polymerising aniline within its intergalleries. The extent of spontaneous polymerisation is limited by the amount of Fe(III) present in the FE. The deliberate polymerisation of remaining anilinium ions by externally introduced oxidant results in highly conductive emeraldine salt-FE (EMS-FE) nanocomposites. The FE host accommodates higher amount of emeraldine salt and the repetitive insertions of the polymer could be done four times for complete layer charge neutralisation whereas with Bentonite the layer charge saturation takes place with three successive insertions. The new EMS-FE nanocomposites exhibit more than order of magnitude greater tuneable ionic and electronic conductivities compared to those of the same polymer incorporated in Bentonite. (c) 2005 Elsevier Ltd. All rights reserved.