Electroless deposition has been used to synthesize a series of Au-, Ag-, and Cu-Pd/SiO2 bimetallic catalysts having incremental surface coverages and compositions of each group IB metal. Thermodynamically unstable, yet kinetically stable, electroless bath(s) were developed using metal bis-cyano salts of the group 1B metal and N2H4 (for Au and Ag) or DMAB (for Cu) as reducing agents. The times (similar to 1-2 h) and profiles (1st order in group 1B metal concentration) observed for complete deposition indicate good kinetic control of the electroless deposition process. The bimetallic catalysts have been characterized using selective chemisorption, atomic absorption spectroscopy (AAS), Fourier transform infrared spectroscopy (FTIR) of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) techniques. Decreases in Pd surface sites with addition of IB metals confirm deposition onto the supported Pd nanoparticle surfaces. FTIR studies suggest that deposition of Cu and Ag are selective towards Pd(1 1 1) sites, while Au deposits non-discriminately on all Pd sites. Finally, XPS measurements for each family of bimetallic catalysts suggest a net electron transfer from the Pd to the deposited metal. (C) 2010 Elsevier B.V. All rights reserved.