Understanding the nature of glass is one of the most important challenges in chemistry, physics, and materials science. In this study, transparent bulk supramolecular glasses with excellent optical behaviors and good mechanical properties were fabricated via the non-covalent polymerization of nucleosides. Hydrogen bonding is the main driving force in the formation of bulk supramolecular glasses. The directional and saturated character of hydrogen bonding enables the formation of a short-range ordered structure, while the weak nature and reversibility of hydrogen bonds allow for the asymmetric and random connections of the short-range ordered structure into a long-range disordered network. Various relaxations, including β, γ, and δ relaxations, are observed at temperatures below the glass transition temperature, demonstrating the metastable nature of bulk supramolecular glasses. This investigation offers supramolecular insights into the nature of glass materials.