AbstractPolysulfur species have been proposed to be the unknown near-UV absorber in the atmosphere of Venus. Recent work argues that photolysis of one of the (SO)₂ isomers, cis-OSSO, directly yields S₂ with a branching ratio of about 10%. If correct, this pathway dominates polysulfur formation by several orders of magnitude, and by addition reactions yields significant quantities of S₃, S₄, and S₈. We report here the results of high-level ab-initio quantum-chemistry computations that demonstrate that S₂ is not a product in cis-OSSO photolysis. Instead, we establish a novel mechanism in which S₂ is formed in a two-step process. Firstly, the intermediate S₂O is produced by the coupling between the S and Cl atmospheric chemistries (in particular, SO reaction with ClS) and in a lesser extension by O-abstraction reactions from cis-OSSO. Secondly, S₂O reacts with SO. This modified chemistry yields S₂ and subsequent polysulfur abundances comparable to the photolytic cis-OSSO mechanism through a more plausible pathway. Ab initio quantification of the photodissociations at play fills a critical data void in current atmospheric models of Venus.