Around 350 references dealing with the use of chiral sulfur ligands for asymmetric catalysis. These reports are clear indication for the efficient use of such ligands promoting numerous catalytic transformations. Their preparation arose from the search for synthetically easily available compounds that were relatively easy to handle and store. Their study is more recent compared to that of P- or N- ligands, although their efficiency for promoting symmetrical catalysis is less impressive. However, they overtake other ligands in terms of activity and enantioselectivity. Additionally, due to their versatility, S,N ligands have a promising future for promoting, especially, C-C bond formations. Due to their stability, the asymmetric heterogenous catalysis is a good way of developing these ligands in an economic and environmentally friendly manner.