Structural development of tellurite glasses with the addition of Li2O and Na2O has been studied using infrared, Raman, and X‐ray photoelectron spectroscopies. The increase in intensity of the peak at 755 cm−1in the infrared spectra as compared to the peak at 620 cm−1suggests the transformation of TeO4building units to TeO3pyramids with the addition of alkali oxide. Proposed structural change is further supported by the strong compositional dependence of the 755‐cm−1peak in the Raman spectra as well as by the formation of a shoulder in the O 1speak of X‐ray photoelectron spectra. In contrast to alkali silicate glasses, formation of nonbridging oxygens with the addition of alkali oxide is n