The synthesis of cyclic thiocarbonates by the cycloaddition of carbon disulfide (CS2) to thiiranes in the presence of silica-immobilized amine catalysts was investigated. The catalytic activities of the silica-immobilized catalysts toward the synthesis of cyclic thiocarbonates were higher than the activities of their homogeneous counterparts. The silica-supported catalysts strongly accelerated the cycloaddition of CS2 to thiiranes, and the pseudo-first-order rate constant of the silica-immobilized catalyst was about 430 times larger than that of the corresponding homogeneous catalyst. The coexistence of the molecular catalyst species and the neighboring surface silanols on the catalyst support was found to be key to the reaction acceleration. In addition to providing improved catalytic activity, the solid-supported catalysts Were also shown to be recyclable and reusable for at least five cycles.