X-ray photoelectron spectroscopy (XPS) coupled with ion beam etching allows the measurements of concentrations gradients at the external surface of concrete. The chemical modifications, caused by the moulding and cleaning operations and due to carbonation, are efficiently investigated. Based on the detection of specific elements (such as chlorine, carbon and silicon), the presence of formworks residues is established on the concrete surface. Similarly, aliphatic (C–(C,H) and carbonaceous (C–O) residues of the demoulding agent can be detected. The concentration gradients show the presence of moulding residues is mainly superficial and decreases rapidly according to the depth. However, certain of these contaminants (and especially polydimethylsiloxane residues) could alter the wetting of aqueous-based coatings. The sandblasting process can partially remove the moulding residues, but the decontamination remains incomplete in spite of the high increase of the roughness of the samples. On the contrary, the concentrations in aliphatic and carbonaceous residues increase after cleaning with solvents, which can be trapped in the pores of concrete to contaminate the surface. The carbonation process is also investigated by XPS. The concentration gradient of the carbonate component of the C 1 s peak shows a front of carbonation progressing as a function of the time after demoulding. Copyright © 2012 John Wiley & Sons, Ltd.