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The silicon oxynitride glasses take advantage of nitrogen bonding to attain high elastic modulus, increased softening temperatures and viscosities, greater slow crack growth resistance, and modest gains in fracture resistance. Of the oxynitride glasses, the Si–Y–Al-based oxynitride glasses have been most extensively studied and a degree of success has been achieved in understanding how changes in glass composition affect structural parameters and their relationship with properties. More recent studies have focused on the Si–RE–Me oxynitride glasses, where Me is primarily Al or Mg and rare earth (RE) includes most of the lanthanide series elements. These glasses possess a range of elastic, thermal, mechanical, and optical properties, which can be correlated with the strength of the RE bond in terms of the cationic field strength. However, such correlations require knowledge of not only the RE valence state but also its coordination with the anions. Herein, the current state-of-the-art understanding of the properties and structural parameters of oxynitride glasses and their interrelationships are reviewed.