Nanoscale electron sources with high electron-emitting performance are of great interest in vacuum nanoelectronics. Resembling traditional thermionic emission sources based on a hot tungsten filament, a hot carbon nanotube or graphene can function as a nanoscale electron source because of its excellent thermal stability and electrical conductivity. In this article, studies of thermionic emission from single hot carbon nanostructures are overviewed, emphasizing their differences in physics from macroscopic thermionic emission as well as potential applications in vacuum nanoelectronics. Due to their low dimensionality, nanoscale size, and nonequilibrium electron distribution, Richardson’s Law, which governs thermionic emission from macroscopic metals, breaks down in the case of thermionic emission from single carbon nanostructures, and an internal electric field in a carbon nanostructure can contribute directly to its thermionic emission. Graphene-based nanoscale thermionic emission sources, source arrays, and vacuum transistors have been fabricated and demonstrated to exhibit the advantages compared to those based on field emission. The advances imply the promise of realizing high-performance nanoscale electron sources and vacuum electronic devices based on thermionic emission.