For nanoparticles active for chemical and energy transformations in static liquid environment, chemistries of surface or near-surface regions of these catalyst nanoparticles in liquid are crucial for fundamentally understanding their catalytic performances at a molecular level. Compared to catalysis at a solid-gas interface, there is very limited information on the surface of these catalyst nanoparticles under a working condition or during catalysis in liquid. Photoelectron spectroscopy is a surface-sensitive technique; however, it is challenging to study the surfaces of catalyst nanoparticles dispersed in static liquid because of the short inelastic mean free path of photoelectrons traveling in liquid. Here, we report a method for tracking the surface of nanoparticles dispersed in static liquid by employing graphene layers as an electron-transparent membrane to separate the static liquid containing a solvent, catalyst nanoparticles, and reactants from the high-vacuum environment of photoelectron spectrometers. The surfaces of Ag nanoparticles dispersed in static liquid sealed in such a graphene membrane liquid cell were successfully characterized using a photoelectron spectrometer equipped with a high vacuum energy analyzer. With this method, the surface of catalyst nanoparticles dispersed in liquid during catalysis at a relatively high temperature up to 150 °C can be tracked with photoelectron spectroscopy.