For several decades an open question in many X-ray photoelectron spectroscopy (XPS) studies was whether or not the results obtained in ultra-high vacuum conditions (UHV) were representative of the sample state in gas atmospheres. As a consequence, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) was received by surface scientists as an important tool for in situ characterization of the gas-solid interactions. However, it is not yet clear how, if at all, the surface state formed in contact with the gas is modified when this gas is evacuated. In this work we compare synchrotron-based XPS results recorded at 300 degrees C on Ni/yttria-stabilized zirconia cermet and La0.75Sr0.25Cr0.9Fe0.1O3 perovskite, under 3.5 mbar O-2 and UHV environments. We found that the surface state formed in O2 is maintained to a large extent under vacuum. In addition, we demonstrate that the correlation of XPS spectra recorded in the two conditions can provide information regarding the electrical conductivity of the specific surface sites of these complex oxides. Our findings suggest that comparison of XPS measurements in gas and in vacuum environments might be particularly useful in applications where the electronic conductivity at the surface plays a crucial role, as for example in solid oxide electrochemical devices. (C) 2017 Elsevier B.V. All rights reserved.