Liquid-vapor interfaces, particularly those between aqueous solutions and air, drive numerous important chemical and physical processes in the atmosphere and in the environment. X-ray photoelectron spectroscopy is an excellent method for the investigation of these interfaces due to its surface sensitivity, elemental and chemical specificity, and the possibility to obtain information on the depth distribution of solute and solvent species in the interfacial region. In this Perspective, we review the progress that was made in this field over the past decades and discuss the challenges that need to be overcome for investigations of heterogeneous reactions at liquid-vapor interfaces under close-to-realistic environmental conditions. We close with an outlook on where some of the most exciting and promising developments might lie in this field.