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X-ray photoelectron spectroscopy (XPS) is a powerful tool for surface and interface analysis, providing the elemental composition of surfaces and the local chemical environment of adsorbed species. Conventional XPS experiments have been limited to ultrahigh vacuum (UHV) conditions due to a short mean free path of electrons in a gas phase. The recent advances in instrumentation coupled with third-generation synchrotron radiation sources enables in situ XPS measurements at pressures above 5 Torr. In this paper, we describe the basic design of the ambient pressure XPS setup that combines differential pumping with an electrostatic focusing. We present examples of the application of in situ XPS to studies of water adsorption on the surface of metals and oxides including Cu (110), Cu (111), TiO 2 (110) under environmental conditions of water vapor pressure. On all these surfaces we observe a general trend …