The reactions between silver and sulfur clusters are studied with a laser double ablation reactor. The main reaction products are [AgS4](+), [AgS8](+), [AgS12](+), and [AgS16](+), which have different compositions from those of Ag/S clusters produced from Ag/S mixed sample by laser ablation. The photolysis of the products with a 193 nm excimer laser indicates that [AgS12](+) and [AgS16](+) have a photodissociation efficiency much higher than that of [AgS4](+) and [AgS8](+). The structure of the products and the mechanism of the reactions to form products [AgS12](+) and [AgS16](+) are discussed.