Tungsten-phosphate glasses doped with trivalent europium ion are synthesized and their spectroscopic properties are analyzed. Following the evolution of the 5D0 → 7F1 electronic transition in a series of various glass compositions via two rank crystal field parameters (cfp’s), a slight modification of the local symmetry is evidenced in the series. Decay lifetimes of 5D1 and 5D0 levels are also analyzed. Optical properties clearly correspond to Eu3+ in the glassy phase. At room as well as at liquid nitrogen temperatures, the emission spectra display comparable features with prominent 5D0 → 7F2 transition. However, at 77 K, the maximum 7F1 splitting exhibits an increase of ≈ 20-23 % for all compounds. This increase is directly connected to a change in local environment around the rare earth ion. The optical properties and the crystal field variation could be correlated with the shortness of the metal-oxygen distances produced by the pressure when cooling.