Sulfur is a promising cathode material that offers exceptionally high capacity, however, it suffers from limited cyclability and a number of other serious issues. Recently, some organic sulfur-containing materials has been demonstrated to be promising alternatives with relatively high capacity while maintaining good cyclability. These materials often dissolve in the electrolyte forming a catholyte solution. In this work, the electrochemistry of various organosulfide molcules in the catholyte is explored using computational techniques. The equilibrium structures and the associated reaction mechanism upon lithiation are determined. It is found that the polysulfide shuttle effect can be greatly suppressed through an on-site trapping mechanism. The electrochemistry can also be tuned by a careful selection of the functional groups that attach to the sulfur chain. These observations help to improve our understanding of the electrochemical behavior of these organosulfides.