New multicomponent glasses in the system WO3-La2O3-B2O3-Nb2O5 doped with Eu3+, as a transparent active media for optical application were obtained. Physical parameters as density, molar volume, oxygen molar volume and oxygen packing density were determined. The thermal behavior of the obtained glasses was examined by differential thermal analysis (DTA). It was established that glass crystallization temperature is about 750oC. Microstructural characterization was made by Raman and UV-VIS spectroscopies. Based on the obtained spectral data short-range order and connectivity in glass network were determined. High photoluminescence emissions due to the 4f transitions 5D0→7Fj (j=0-4) of Eu3+ ions were observed. Colorless bulk tungstate glass, containing Nb2O5 with high transparency and high refractive index were prepared.