Multifunctional hyperbranched polymers have found wide applications in diverse areas. However, the preparation of these polymers is generally under harsh polymerization conditions with limited reactions. In this work, we prepared multifunctional hyperbranched poly(vinylene sulfide)s (hb-PVSs) by our established efficient and spontaneous thiol-yne click polymerization for the first time. A series of hb-PVSs with high molecular weights (M-w up to 63100) were obtained in high yields (up to 86%) from the polymerizations of monomers 1 and 2 with equivalent molar ratio in THF at 20 degrees C for 2 h. All the hb-PVSs are regioregular, soluble, and thermally stable. Thanks to the unreacted ethynyl groups on their peripheries, the hb-PVSs could be facilely functionalized by consecutive thiol-yne click reactions. Moreover, the solid films of hb-PVSs exhibit higher refractive index (RI) values (n > 1.64) than those of traditional optical plastics. The TPE-containing hb-PVS shows unique aggregation-enhanced emission characteristic and its aggregates could be used to detect explosives with superamplification effect. Therefore, this work not only proves the universality of our developed spontaneous thiol-yne click polymerization but also provides a powerful and versatile platform for the preparation of multifunctional sulfur-containing polymers.