This study presents a novel approach to constructing bulk transparent supramolecular glass using host–guest molecular recognition motifs between methyl-β-cyclodextrin (M) and para-hydroxybenzoic acid (H). The non-covalent polymerization of these host–guest complexes and hydrogen bonding forms a high-transparency, bulk-state supramolecular glass. The glass exhibits various advantages, including recyclability, compatibility, and thermal processability. The structural analysis reveals short-range order (host–guest complexation) and long-range disorder (three-dimensional polymeric network), typical of glass. The study highlights the potential of supramolecular glasses as a new class of transparent materials with organic components, offering a universal design concept for transparent supramolecular materials.This study presents a novel approach to constructing bulk transparent supramolecular glass using host–guest molecular recognition motifs between methyl-β-cyclodextrin (M) and para-hydroxybenzoic acid (H). The non-covalent polymerization of these host–guest complexes and hydrogen bonding forms a high-transparency, bulk-state supramolecular glass. The glass exhibits various advantages, including recyclability, compatibility, and thermal processability. The structural analysis reveals short-range order (host–guest complexation) and long-range disorder (three-dimensional polymeric network), typical of glass. The study highlights the potential of supramolecular glasses as a new class of transparent materials with organic components, offering a universal design concept for transparent supramolecular materials.