Vacuum ultraviolet excitation spectra of phosphors (La,Gd)PO4:RE3+ (RE = Eu or Tb) and X-ray photoelectron spectra of LaPO4 and GdPO4 are investigated. The vacuum ultraviolet excitation intensity of (La,Gd)PO4:RE3+ is enhanced with the increasing of Gd3+ content, which implies that Gd3+ plays an intermediate role in energy transfer from host absorption band to RE3+. When Gd3+ is doped into LaPO4:Eu, charge transfer band (CT band) begins to shift to higher energy region and the overlap degree of CT band and the host absorption band gets greater with more Gd3+ doped into LaPO4. These results suggest that the dopant (Gd3+) gives an important influence on energy transfer efficiency. The top of LaPO4 valance band is formed by the 2p level of O2-, whereas that of GdPO4 valance band is formed by the 2p level of O2- and the 4f level of Gd3+, showing the differences in band structures between LaPO4 and GdPO4. (C) 2002 Elsevier Science Ltd. All rights reserved.