A new charge neutralization method for monochromatized X-ray photoelectron spectroscopy was proposed. The point of this method is to mount metal walls around the sample. As X-ray photons irradiate the walls, the electrons which neutralize the surface charge of the sample are emitted. With the metal walls of the high secondary electron emissive materials, the peak shift of the Al2p XPS spectrum for sapphire was smaller than 10 eV; furthermore the differential charging of roughed sapphire surfaces was eliminated. This method can be widely used without complicated adjustment, and is more useful and effective than conventional methods.