Hoop-shaped or belt-like molecules have been fascinating not only due to their challenging synthesis, but also unique physical and chemical properties. The incorporation of heteroatoms (N, O, S, etc.) into these belts could alter both molecular structures and electronic properties which will lead to versatile applications, from advanced host-guest systems to functional materials. Despite numerous computational studies, the synthesis and characterization of heteroatom-bridged double-stranded

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... cular belts remains scarce. Here we report the synthesis, crystal structure, and host-guest chemistry of two novel heteroatom-bridged belt-like macrocycles composed of phenoxathiin. The bowl-shaped belt demonstrates a strong binding affinity (Ka = 3.6 × 109 M‒2) towards fullerene C60 and forms a 2:1 capsule-like complex with the aid of C‒H···S hydrogen bonds. The column-like belt can bind the cyclic guest [2,2]paracyclophane to form a ring-in-ring complex. The modular synthesis, structural specificity, and diverse host-guest chemistry of cyclophenoxathiins markedly expands the known chemistry of molecular belts.