Photoemission behaviors of nano-CeO2 films with particle sizes ranging from 8nm 1o50nm and bulk CeO2 in Ce 4d-4f absorption region have been investigated. Resonantenhancements of Ce 4f valance band and Ce 5p bands for nano film and bulk materialhave been observed. The variation of electron density of states in valance bands ofnano and bulk structures of CeO2 is discussed in terms of Ce 4d-4f resonance.