Co-sputtered Pd(0.7)Au(0.3) catalyst and alternate sputtered Pd(0.35)Au(0.3)Pd(0.35) and Au(0.15)Pd(0.7)Au(0.15) materials were prepared by plasma deposition of Au and Pd atoms on a carbon diffusion layer. Atomic composition and metal loadings were evaluated from EDX and RBS, respectively. The low amount of metal deposited and the resulting low metallic film thickness made TEM and XRD characterizations difficult to perform, therefore, catalyst microstructures and surface compositions were determined from electrochemical methods and compared with data obtained with Pd/C, Au/C and Pd(0.7)Au(0.3)/C materials synthesized via the "water in oil" microemulsion method. The surfaces of co-sputtered Pd(0.7)Au(0.3) and alternate sputtered Pd(0.35)Au(0.3)Pd(0.35) and Au(0.15)Pd(0.7)Au(0.35) materials are partly composed by PdAu alloy. The plasma sputtering method leads to more active bimetallic PdAu material than the wet chemistry method. Modification of palladium surface by gold atoms leads to increase the catalytic activity toward glycerol electrooxidation. The PdAu surface alloy composition has no significant effect on the catalytic activity, however, the presence of non-alloyed gold sites on the material surface leads to the enhancement of the catalytic activity. The mechanism seems to involve glycerol adsorption on palladium surface and hydroxyl species formation on gold surface leading to catalytic activity enhancement through the bifunctional mechanism. (C) 2011 Elsevier B.V. All rights reserved.