The local structure and the valences of europium in SrBPO5:Eu prepared in air were checked by means of XAFS at Eu–L3 edge. From the EXAFS results, it was discovered that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu–O were 2.42Å in the host. From the XANES data, it was found that the divalent and trivalent europium coexisted in the matrix. The emission spectra excited by VUV or UV exhibited a prominent broad band due to the 4f65d–4f7 transition of Eu2+ ions, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [VSr]″ formed by aliovalent substitution between Sr2+ and Eu3+ ions. The VUV excitation spectra in 100–200nm range showed that the matrix had absorption bands with the maxima at about 130 and 150nm, respectively.