AbstractFour complexes of MCl4 (M=Ti, Zr, Hf) with the hypervalent trifluoromethyl iodine reagent trifluoromethyl‐1,3‐dihydro‐3,3‐dimethyl‐1,2‐benziodoxole (1,=L) are described. With TiCl4, an I−O bond cleavage occurs, leading to the formation of the trifluoromethyliodonium alcoholate complexes [Ti2Cl6(L)4]Cl2 (2 a) and Ti2Cl8(L) (2 b). Reactions with ZrCl4 and HfCl4 form the complexes ZrCl4(L)2 (3) and HfCl4(L)2 (4), respectively, wherein the original I−O bond is retained and elongated compared to that in free 1. Therefore, the reactivity of 1 can be easily and practically fine‐tuned by addition of different metal chlorides, following the order ZrCl4/HfCl4<TiCl4<2 TiCl4. Complexes 2 a, 3, and 4 are remarkably bench‐stable forms of activated reagent 1, while 2 b is readily accessible in situ. 2 a and 2 b represent the first “real” trifluoromethyliodonium reagents derived from iodanes, that is, with the I−O bond being completely cleaved. The new complexes were shown to be useful for the trifluoromethylation of para‐toluenesulfonate under aprotic conditions.