In rare-earth-doped silica optical fibres, the homogeneous distribution of amplifying ions and part of their spectroscopic properties are usually improved by adding selected elements, such as phosphorus or aluminum, as structural modifier. In erbium ion (Er3+) doped fibres, phosphorus preferentially coordinates to Er3+ ions to form regular cages around it. However, the crystalline structures described in literature never gave particular spectroscopic signature. In this article, we report emission and excitation spectra of Er3+ in a transparent phosphorus-doped silica fibre preform. The observed line features observed at room and low temperature are attributed to ErPO4 crystallites.