Recent advances in the chemistry of all the well-known chiral ferrocynyl phosphines in homogeneous catalysis, with a special thrust to consolidate all the important work in this area are highlighted. A conscious attempt to provide the necessary background, basic principles, and some history, with a view to help readers who are not well exposed to this area is made. Importance is given to the applications, such as asymmetric coupling, allylations, C=C, C=O, and C=N hydrogenations, hydrogen transfer, and other synthetically relevant reactions.