In the present work, CaP4O11 was explored as a host material of phosphors for solid-state lighting applications for the first time. This ultraphosphate compound doped with Eu3+ ions was prepared via the solid-state reaction in air atmosphere. The photoluminescence properties were investigated under (UV) ray excitation. From a powder X-ray diffraction analysis, structural Rietveld refinement and IR/Raman spectroscopy, the formation of single phase CaP4O11 with a monoclinic structure was confirmed. The spectral distribution of the Eu3+ -doped CaP4O11 ultraphosphate results in an overall orange-red emission due to the non-negligible intensity of the 5D0→7F1 transition. One Eu3+ center was attributed according to the crystal structure and the luminescence characteristics. The luminescence decay curve of CaP4O11:Eu3+ was fitted into a single exponential function and the lifetime was about 3.8 ms. The obtained CaP4O11:Eu3+ phosphors may have a potential application for solid state lighting based on light emitting diodes technology.