Long rooted in its central dogma of DNA → RNA → protein, molecular biology is now outgrowing this linear framework. Glycans are emerging as “molecular keys” that drive the paracentral dogma, which positions glycosylation as a core regulatory layer alongside nucleic acids and proteins. This special issue centers on this conceptual shift, sparked by Wei Wang’s provocative question: “Can DNA be glycosylated?” The discovery of glycoRNAs, the first validated glycan keys, is reshaping our understanding of immune signaling, while putative DNA glycosylation points to a new dimension of epigenetic control. We have invited interdisciplinary contributions addressing glycan-based mechanisms, biomarkers, and enabling technologies and now invite readers to join us in exploring this uncharted territory. The future of molecular medicine is not written solely in codons; it also lies in the precise “teeth” of glycan keys.