The cationic ruthenium half-sandwich complex [Cp*Ru(PPh3)(2)(CH3CN)][OTf] (2) (CP* = eta(5)-C5Me5, OTf = SO3CF3) was synthesized by reduction of [Cp*RuCl2](2) with zinc in the presence of NaOTf and subsequent reaction with PPh3. When NaOTf was omitted, the corresponding tetrachlorozincate salts were obtained. Complex 2, as well as the salts [Cp*Ru(CH3CN)(3)](2)[ZnCl4] (3) and [Cp*Ru(PPh3)(2)(-)(CH3CN)](2)[ZnCl4] (4), were characterized by single-crystal X-ray analysis. Complex 2 proved to be a potent catalyst for the atom transfer radical addition of CCl4 and CHCl3 to terminal olefins, displaying a performance superior to that of the previously described neutral catalyst [Cp*RuCI(PPh3)(2)]. For the addition of CHCl3 to styrene, a total turnover number of 890 was achieved. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).