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Because of the amphiphilic properties of alcohols, hydrophobic hydration is important in the alcohol–water system. In the present paper we employ X-ray photoelectron spectroscopy (XPS) to investigate the bulk and surface molecular structure of ethanol–water mixtures from 0.2 to 95 mol %. The observed XPS binding energy splitting between the methyl C 1s and hydroxymethyl C 1s groups (BES_[CH₃–CH₂OH]) as a function of the ethanol molar percentage can be divided into different regions: one below 35 mol % with higher values (about 1.53 eV) and one starting at 60 mol % up to 95 mol % with 1.49 eV as an average value. The chemical shifts agree with previous quantum mechanics/molecular mechanics (QM/MM) calculations [Löytynoja, T.; J. Phys. Chem. B 2014, 118, 13217]. According to these calculations, the BES_[CH₃–CH₂OH] is related to the number of hydrogen bonds between the ethanol and the surrounding molecules. As the ethanol concentration increases, the average number of hydrogen bonds decreases from 2.5 for water-rich mixtures to 2 for pure ethanol. We give an interpretation for this behavior based on how the hydrogen bonds are distributed according to the mixing ratio. Since our experimental data are surface sensitive, we propose that this effect may also be manifested at the interface. From the ratio between the XPS C 1s core lines intensities we infer that below 20 mol % the ethanol molecules have their hydroxyl groups more hydrated and possibly facing the solution’s bulk. Between 0.1 and 14 mol %, we show the formation of an ethanol monolayer at approximately 2 mol %. Several parameters are derived …