Rh0.5Pd0.5/CeO2 bimetallic nanoparticles were subjected to reducing and oxidizing atmospheres at different temperatures and characterized by means of the Ambient Pressure X-Ray Photoelectron Spectroscopy (AP-XPS). The surface atomic population is calculated for all cases. By using a high temperature pretreatment at 480 degrees C in H-2 atmosphere, it was possible to control the surface atomic population with Pd atoms frozen at the skin layer even in an oxidizing atmosphere, which is not observed without high temperature pre-treatment (Rh atoms at the skin layer). The change of the Rh/Pd surface segregation behavior after the high temperature pre-treatment is attributed to the geometrical factor of Strong Metal Support Interaction (SMSI) effect, i.e., the occurrence of the ceria capping layer around nanoparticles. (C) 2015 Elsevier B.V. All rights reserved.