The chemistry of tetramethyldisiloxane (TMDS) is largely composed of the reduction of functional groups with increasing applications for carbon–carbon bond formation. This reagent can be a safe alternative to H2, LiAlH4, and other reactive reagents. Notable are the amide conversion to amines and aldehydes, nitro group reductions, nitrile reductions, hydrogenolysis of aryl-chlorine bonds, reductive formation of sulfides, reductive etherification, reductive opening of ketals, reductive demethoxylation, and formation of nitriles with homologation. Selectivity can be carried out by the choice of catalysts. This review of recent chemistry will focus on synthetically applied reactions of the recent past. Displayed reactions are chosen to be representative of the referenced work but are also chosen to illustrate a new viewpoint. Finally, where applicable, the results of competing hydrosilanes are presented to compare to the results obtained with TMDS.