Heteracalixaromatics or heteroatom-linked calix(het)arenes are privileged macrocyclic hosts in supramolecular chemistry because they are readily prepared by means of efficient synthetic methods including one-pot macrocyclization approach and step-wise fragment coupling strategy both starting from inexpensive and commercially available materials. Regulated by the bridging nitrogen and oxygen atoms through their electronic interplay with adjacent aromatic rings, heteracalixaromatics adopt interesting conformational structures and exhibit powerful and versatile capability of binding electron neutral and charged guest species with excellent selectivity. As a member of heteracalixaromatics, azacalix [n]pyridines also show great reactivity of pyridine rings toward electrophiles attributable to the strong conjugation effect of bridging nitrogen atoms with pyridines. This would enable the selective installation of bromine substituents at the bay areas, producing ideal predisposed macrocyclic conformation for multiple transition metal-mediated carbon-carbon bond homocoupling reactions to afford zigzag-type aromatic nanobelts (Fig. ).