Sol–gel route has successfully been used to synthesize pure and Eu3+ doped polycrystalline samples of the GdP5O14 pentaphosphates. The as-prepared samples have structurally been characterized using X-ray diffraction. Optical properties in the vacuum ultraviolet (VUV) of Eu3+ activated GdP5O14 samples prepared either by sol–gel process or solid-state reaction were investigated at room temperature for comparison. In this GdP5O14 host matrix the P5O14 ultraphosphate groups were proved to exhibit an efficient absorption in the VUV range. The excitation spectra recorded in the VUV-UV spectral region from 120 nm to 350 nm have revealed the presence of Gd3+ 4f–5d interconfiguration transitions, Gd3+–O2− and Eu3+–O2− charge transfer states(CTS)in addition to intraconfiguration transitions of Gd3+ ions.Furthermore the Gd3+→Eu3+ energy transfer process was investigated and discussed in the framework of the multiphonon relaxation process. Besides, the GdP5O14:Eu3+ phosphor led to a strong red emission under 147/172 nm excitation, so that it can be considered as a promising red phosphor for mercury-free lamps and plasma display panels applications.