Thiol-yne click polymerization (TYCP) is one of the most significant synthetic techniques for artificial polymers, due to its simplicity, efficiency, and functionality tolerance. In nature, it is a classic nucleophilic addition reaction and a step-growth polymerization, which can be initiated or accelerated in the presence of free-radicals, amines, and transition metals, respectively. Its rate is greatly influenced by the structures (i.e., their electrophilicity and steric hindrance) of the used thiols and/or alkynes. With aliphatic monomers being used as feeding materials, the topological architectures (such as linear, branching, and cross-linked network, etc.) and available functional groups (such as hydroxyl, carboxyl, amino, and epoxy groups, and so on) can be facilely tailored via altering the chemical structure and feeding order. In contrast, for aromatic monomers, mono-addition occurs only during the process of thiol-yne click reaction, leading exclusively to linear poly(vinyl thioether)s. These sulfur-containing polymers synthesized by TYCP are promising to be widely utilized as high refractive index materials, photovoltaic materials, drug-delivery vehicles, biomaterials, and hybrid materials, etc.