The need of space-resolved x-ray photoelectron spectroscopy (XPS) has developed scanning photoelectron microscopy (SPEM). SPEM provides space-resolved XPS data from a spot of a sample as well as images of specific element, chemical state, valency distribution on the surface of a sample. Based on technical advancement of tight x-ray focusing, sample positioning accuracy, and electron analyzer efficiency, SPEM is now capable of providing ~100 nm space resolution for typical XPS functionality, and SPEM has become actively applied for the investigation of chemical state, valency, and electronic structure on the surface of newly discovered materials, such as graphene layers, dichalcogenide 2D-materials, and heterogenous new functional materials.