Highlights</br> • Reduced S-rich gas reacts rapidly to form sulfides at the surface of Mercury.</br> • Sulfidation of forsterite and diopside forms MgS, CaS, and quartz.</br> • Volume changes in the regolith due to sulfidation affect hollow formation.</br> </br> Abstract: </br> The surface of Mercury is enriched in sulfur, with up to 4 wt.% detected by the NASA MESSENGER mission, and has been challenging to understand in the context of other terrestrial planets. We posit, that magmatic S was mobilized as a gas phase in volcanic and impact processes near the surface, exposing silicates to a hot S-rich gas at reducing conditions and allowing conditions for rapid gas-solid reactions. Here, we present novel experiments on the reaction of Mercury composition glasses with reduced S-rich gas, forming Ca- and Mg-sulfides. The reaction products provide porous and fragile materials that create previously enigmatic hollows on Mercury. Our model predicts that the gas-solid reaction forms Ca-Mg-Fe-Ti-sulfide assemblages with SiO2 and aluminosilicates, distinct from formation as magmatic minerals. The ESA/JAXA BepiColombo mission to Mercury will allow this hypothesis to be tested.