In recent years, chalcogen bonding (ChB) has emerged as a developing and versatile tool for the bottom-up construction of functional nanostructures on surfaces. This minireview systematically explores the fundamental principles and recent advancements in ChB-directed on-surface synthesis. We highlight how ChB, characterized by its strong directionality and tunable interaction strength, complements conventional noncovalent interactions (hydrogen bonds, halogen bonds, and metal-ligand coordination) in engineering well-defined low-dimensional architectures. Key findings demonstrate ChB’s unique capabilities in driving molecular recognition, controlling topology selectivity in conformationally flexible precursors, and facilitating disorder-to-order transitions in two-dimensional networks. Particularly, we discuss how surface confinement modifies ChB properties, enabling novel assembly pathways and reactivity in on-surface synthesis. By bridging fundamental ChB interactions and the practical implementation in on-surface nanotechnology, this minireview provides valuable insights for designing functional nanomaterials through rational ChB engineering, while outlining current challenges and future directions in this emerging field.
