Silver nanoparticles are known and widely used for their antimicrobial activities. Nevertheless, once they are released into the natural or biological environments, they can become toxic with time, because of the dissolution of some Ag(I) ions that can then react with thiol-based molecules, such as glutathione and/or compete with copper proteins. These assumptions are based on the high affinity of the soft acid Ag(I) and the soft base thiolates and the exchange reactions that are involved in complex physiological media. Here we synthesized and fully characterized two new 2D silver thiolate coordination polymers (CPs) that exhibit a reversible 2D-to-1D structural transformation in the presence of an excess of thiol molecules. This dimensionality change induces also a switch of the yellow emission of the Ag-thiolate CP. This study highlights that these highly stable silver-thiolate CPs, in basic, acidic and oxidant media can undergo a complete dissolution-recrystallization mechanism upon thiol exchange reactions.