In this work, PdAg/Al2O3 composite membranes prepared by electroless co-deposition technique have been studied. Effects of plating time, Ag composition and total concentration of metal ions on surface morphologies, composition and microstructure of the resulting layers were investigated. Scanning electron microscope, energy dispersive spectrometer and nitrogen permeation technique were used to characterize the as-prepared composite membranes. From the experimental results, it shows that the surface morphology of the deposited PdAg layer is strongly affected by the Ag content of the plating bath. Since large differences of deposition rates and growth modes are observed between Pd and Ag grains, the PdAg layer exhibits the dendritic structure. As the Ag content is approximately 50%, the dendritic structured PdAg layer reveals the largest nitrogen permeability with the smallest size of residual pores. Furthermore, a comprehensive electrochemical analysis is proposed to interpret the composition and structure of the PdAg layer. Eventually, the experimental results are quite consistent with those predicted from the electrochemical analysis. (C) 2004 Elsevier B.V. All rights reserved.