Conventional electron microscopy during the last three decades has experienced tremendous developments, especially in equipment design and engineering, to become one of the most widely recognized and powerful tools for key research areas in materials science and nanotechnology. In this article, we discuss scanning ultrafast electron microscopy (S-UEM) as a new methodology for four-dimensional electron imaging of material surfaces. We also illustrate a few unique applications. By monitoring secondary electrons emitted from surfaces of photoactive materials, photo- and electron-impact-induced electrons and holes near surfaces, interfaces, and heterojunctions can be imaged with adequate spatial and temporal resolution. Charge separation, transport, and anisotropic motions as well as their dependence on carrier energies can be resolved. S-UEM is poised to directly image and visualize relevant interfacial dynamics in real space and time for emerging optoelectronic devices and help push their performance.