Monometallic Au, Pd and bimetallic Au-Pd catalysts supported on a Ce0.62Zr0.38O2 mixed oxide have been synthesized by the sol-immobilization method. An in-depth Scanning-Transmission Electron Microscopy (STEM) study has been performed to reveal the structural and chemical nature of the metal nanoparticle system present in these catalysts. Attention has been paid both to the evolution of the particle size distribution and the degree of Au-Pd interaction as a function of the treatment used to activate the catalysts. This characterization work has been complemented by results coming from other macroscopic techniques like Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), N-2 physisorption, Temperature Programmed Oxidation (TPO) or X-ray Photoelectron Spectroscopy (XPS). The whole set of characterization data evidences the intrinsic structural complexity of this type of bimetallic systems, in which a fraction of monometallic Au, monometallic Pd and bimetallic nanoparticles of varying compositions coexist. This picture, which clearly contrasts with other much more homogeneous situations described in previous literature on bimetallic catalysts, also indicates the requirement of combining both atomic scale and macroscopic techniques to understand the structure of these catalysts. Concerning catalytic performance, a synergistic effect between Au and Pd has been observed in the selective oxidation of benzyl alcohol on ceria-zirconia. Moreover, the catalytic activity of these bimetallic Au-Pd catalysts is higher than that on other commonly used supports, such as activated carbon or carbon nanotubes. The treatments in oxidative and inert atmospheres at 250 degrees C improve the catalytic activity with respect to the fresh, un-pretreated, catalyst. Subsequent reduction of the oxidized bimetallic catalyst leads to an activity similar to that of the fresh catalyst, which is reduced at room temperature with H-2 bubbles. (C) 2016 Elsevier B.V. All rights reserved.