Recent advances in the catalytic one-electron reduction are the subject of this account. A titanium-, vanadium- or chromium-catalyzed reduction reaction including dehalogenation, pinacol coupling, the McMurry coupling, the related radical cyclization, and the Nozaki-Hiyama-Kishi reaction has been developed by constructing a multi-component system in combination with a co-reductant and additives, which serve for the liberation of the catalyst and the facilitation of the recycling steps. The high stereoselectivity is allowed to be attained in some catalytic reductive bond formations.