Herein, a series of novel sulfur-containing functionalized disiloxanes based on a low-cost and commercially available material, i.e., 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and various thiol compounds were prepared by thiol–epoxy click reaction. It was found that both lithium hydroxide (LiOH) and tetrabutylammonium fluoride (TBAF) have high catalytic activity after optimizing the reaction condition, and the reaction can be carried out with high yields, excellent regioselectivity, mild reaction condition, and good tolerance of functional groups. These compounds exhibit excellent nonconventional fluorescence due to the formation of coordination bonds between Si atoms and heteroatoms (e.g., S or N) and can emit blue fluorescence upon ultraviolet (UV) irradiation. These results demonstrate that the thiol–epoxy click reaction could promisingly act as an efficient organosilicon synthetic methodology to construct various organosilicon materials with novel structures and functionality, and thus their application scope will be significantly expanded.