An ordered germanium terminated (1 0 0) diamond surface has been formed and characterised using a combination of low energy electron diffraction and synchrotron-based core level photoemission spectroscopy. A number of preparation methods are explored, in each case inducing a two domain [Formula: see text] surface reconstruction. The surface becomes saturated with bonded germanium such that each [Formula: see text] unit cell hosts 1.26 Ge atoms on average, and possesses a negative electron affinity of -0.71 eV.