Sulfur-chlorine cycles play a role in the atmosphere of Venus. It is thought that many sulfur-chlorine bearing molecules could be present in Venus's atmosphere and play an important role in its chemical processes. The goal of this work is to provide new insight into the electronic structure and spectroscopy of the [Cl, S, S, O] molecular system. Eight isomers could be formed, but only three were found to be thermodynamically stable relative to the first dissociation limit. We spectroscopically characterized the two lowest energy stable isomers, C1-ClSSO and trans-ClSSO, using the accurate CCSD(T)-F12/aug-cc-pVTZ method. The dipole moments of the two lowest energy stable isomers are predicted to be 1.90 and 1.60 debye, respectively. The C1-ClSSO isomer is suitable for laser induced fluorescence detection since the lowest excited electronic states absorb in the visible, ∼610 nm, and near UV region, 330 nm. We mapped the evolution of the low-lying excited electronic states along the ClS, SS, and SO bond lengths to find that the production of ClS, SO, or S2O is plausible, whereas the production of ClS2 is not allowed.