The structures of the band gap and defect states of chemical-vapor-deposited diamond films were investigated by photoluminescence spectroscopy, covering wavelength from visible to vacuum ultraviolet (VUV). Band gaps ranging from 5.5 to 3.2 eV were measured for natural, polycrystalline, and amorphous diamond films. Low voltage field emissions were obtained from wide band gap films with band gap states distributed close to the conduction band and extended deeply into the band gap. Amorphous diamond film with a narrower band gap could not provide low field emission.