Accurate multireference configuration interaction and time-dependent density functional calculations have been performed to interpret the experimental UV-vis spectrum of the CS2/Cl complex in the spectral region 320-550 nm. The molecular structure of the complex responsible for the previously observed UV-vis spectrum is recognized as ClSCS, not CICS2. Two low-lying excited states of ClSCS, responsible for its optical absorption, have been identified and analyzed. Optical excitation of ClSCS leads to the excitation-specific bond elongation that may lead to photofragmentation of the molecule. In addition, experimental conditions for verifying the presence of ClCS2 are identified and detailed characterization of its optically active excited states with possible photofragmentation pathways is given.