The thermionic emission properties of the borides of the alkaline‐earth and rare‐earth metals and thorium have been investigated. These compounds all have the same formula MB6and the same crystal structure consisting of a three‐dimensional boron framework in whose interlattice spaces the metal atoms are embedded. The valence electrons of the metal atoms are not accepted by the B6complex, thus giving rise to the presence of free electrons which impart a metallic character to these compounds. This, together with the strong bonds between the boron atoms in the framework, produces a series of compounds which have high electrical conductivities and high thermal and chemical stabilities—ideal properties for a cathode material. When this structure is heated to a sufficiently high temperature, the metal atoms at the surface evaporate away. They are, however, immediately replaced by diffusion of metal atoms from the underlying cells. The boron frame work does not evaporate but remains intact. This process gives a mechanism for constantly maintaining an active cathode surface. Thermionic emission measurements made on these materials show the rare‐earth metal borides to be superior to the others. The highest emission was obtained from lanthanum boride. Its emission constants for the Dushman equation were &fgr;=2.66 volts andA=29 amps/cm2/degK2. This is higher than the emission normally obtained from thoria. Lanthanum boride has a relatively low evaporation rate corresponding to a latent heat of evaporation of 169 kilocalories per mole. If the hexaborides are operated at high temperature in contact with the refractory metals, boron diffuses into their metal lattices forming interstitial boron alloys with them. When this occurs, the boron framework which holds the alkaline‐earth or rare‐earth metal atoms collapses, permitting the latter to evaporate. However, the hexaboride cathodes may be operated at high temperatures in contact with tantalum carbide or graphite. Lanthanum boride cathodes are especially useful in applications where high current densities are required. They are also suitable for high voltage applications because they stand up well under positive ion bombardment. Since they are atmospherically stable and activate easily, they have found wide use in experimental demountable systems.