Recent photoemission studies on heavily boron-doped superconducting diamond films, reporting the electronic structure evolution as a function of boron concentrations, are reviewed. From soft X-ray angle-resolved photoemission spectroscopy, which directly measures electronic band dispersions, depopulation of electrons (or formation of hole pockets) at the top of the valence band were clearly observed. This indicates that the holes at the top of the valence bands are responsible for the metallic properties and hence superconductivity at lower temperatures. Hard X-ray photoemission spectroscopy observed shift of the main C Is core level and intensity evolution of a lower binding energy additional structure, suggesting chemical potential shift, carrier doping efficiency by boron doping, and possibility of boron-related cluster formations.