The kinetics and products of a range of reactions between six different nucleophiles of varying gas phase basicities and dimethoxydisulfide and diethoxydisulfide were studied in a flowing afterglow apparatus. Several different types of reactions have been observed, many of which result in the formation of new sulfur containing anions. These reactions include: cleavage of the sulfur-sulfur bond to form ROS−ions, elimination to give ROSS−ions and attack at carbon to yield ROSSO−ions. For some nucleophiles (HA−), anions of the type HAS, ROSA−, and ROSSA−are also formed. An unified reaction scheme is proposed to account for the formation of each of the product ions and comparisons with the solution phase reactivity of dialkoxydisulfides are made. In addition, the dialkoxydisulfides have been subject to electron impact (EI) in the negative ion mode. The major product ions are the alkoxydisulfide anions, ROSS−. The reactivity of these alkoxydisulfide anions towards several neutral reagents has been probed. Both anions are fairly unreactive, consistent with their low gas phase basicity.