The microstructures of thin coating films of pure palladium and palladium alloys deposited from organic electrolytes onto different metallic substrates by electroless plating method have been investigated. The coatings are dense, pore-free 0.005-1 mu m thick films with high adhesive strength to the substrate surface. X-ray spectral analysis, X-ray phase analysis, transmission and scanning electron microscopy were used to determine the composition and structure of alloy coatings of binary systems: Pd-Au, Pd-Ag, Pd-Ni, Pd-Pb, and ternary system Pd-Au-Ni. The coatings of Pd-Au, Pd-Ag, and Pd-Ni have a solid solution structure, whereas Pd-Pb is intermetallic compound. It has been found that the deposited films consist of nanocrystalline grains with sizes in the range of 11-35 nm. Scanning and transmission electron microscopy investigations reveal the existence of clusters formed by nanocrystalline grains. The origin for the formation of nanocrystalline structures of coating films is discussed. (C) 2009 Elsevier B.V. All rights reserved.