X-ray photoelectron spectroscopy (XPS) is a popular analytical technique in materials science as it can assess the surface chemistry of a broad range of samples. This Primer concerns best practice in XPS analysis, aimed at both entry-level and advanced users, with a focus on thin film samples synthesized under vacuum conditions. The high surface to volume ratio of thin films means that factors such as substrate choice and air exposure time are important for the final result. Essential concepts are introduced, such as binding energy, photoelectric effect, spectral referencing and chemical shift, as well as practical aspects including surface sensitivity, probing depth, energy resolution, sample handling and sputter etching. Correct procedures for experimental planning, instrument set-up, sample preparation, data acquisition, results analysis and presentation are reviewed in connection with physical principles and common applications. Typical problems, including charging, spectral overlap, sputter damage and binding energy referencing, are discussed along with possible solutions or workarounds. Finally, a workflow is presented for arriving at high-quality results. X-ray photoelectron spectroscopy (XPS) can be used to investigate chemical bonding and elemental composition. This Primer discusses how XPS can be used to characterize thin films, including key considerations for sample preparation, experimental set-up and data analysis.