Secondary electron emission serves as the foundation for a broad range of vacuum electronic devices and instrumentation, from particle detectors and multipliers to high-power amplifiers. While secondary yields of at least 3–4 are required in practical applications, the emitter stability can be compromised by surface dynamics during operation. As a result, the range of practical emitter materials is limited. The development of new emitter materials with high yield and robust operation would advance the state-of-the-art and enable new device concepts and applications. In this Perspective article, I first present an analysis of the secondary emission process, with an emphasis on the influence of material properties. From this analysis, ultra-wide bandgap (UWBG) semiconductors and oxides emerge as superior emitter candidates owing to exceptional surface and transport properties that enable a very high yield of low-energy electrons with narrow energy spread. Importantly, exciting advances are being made in the development of promising UWBG semiconductors such as diamond, cubic boron nitride (c-BN), and aluminum nitride (AlN), as well as UWBG oxides with improved conductivity and crystallinity. These advances are enabled by epitaxial growth techniques that provide control over the electronic properties critical to secondary electron emission, while advanced theoretical tools provide guidance to optimize these properties. Presently, H-terminated diamond offers the greatest opportunity because of its thermally stable negative electron affinity (NEA). In fact, an electron amplifier under development exploits the high yield from this NEA surface, while more robust NEA diamond surfaces are demonstrated with potential for high yields in a range of device applications. Although c-BN and AlN are less mature, they provide opportunities to design novel heterostructures that can enhance the yield further.