Abstract Characterization of B 2 O 3 and/or WO 3 containing tellurite glasses was realized in the 0.80TeO 2 –(0.20 − x )WO 3 − x B 2 O 3 system (0 ≤ x ≤ 0.20 in molar ratio) by using differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectrometry techniques. Glasses were prepared with a conventional melt-quenching technique at 750 °C. To recognize the thermal behavior of the glasses, glass transition and crystallization temperatures, glass stability value, glass transition activation energy, fragility parameter were calculated from the thermal analyses. Density, molar volume, oxygen molar volume and oxygen packing density values were determined to investigate the physical properties of glasses. Fourier transform infrared spectra were interpreted in terms of the structural transformations on the glass network, according to the changing B 2 O 3 and/or WO 3 content. Crystallization behavior of the glasses was investigated by in situ X-ray diffraction measurements and microstructural characterization was realized by scanning electron microscopy and energy dispersive X-ray spectrometry analyses.