Abstract The reactions of various alkylantimony compounds with titanium chlorides have been investigated. Tetraethylstibonium chloride was found to react with titanium tetrachloride to give the complex salts [SbEt4]2TiCl6 (I), [SbEt4]TiCl5 (II) and [SbEt4]Ti2Cl9 (III), and with titanium trichloride to give the complex salts [SbEt4]2TiCl5 (VI) and [SbEt4]TiCl4 (V). Titanium dichloride was oxidized by tetraethylstibonium chloride to form the complex salts of tervalent titanium, IV and V. Triethylantimony dichloride made addition with titanium tetrachloride and afforded two or more ionic complexes, SbEt3Cl2·TiCl4 and (SbEt3Cl2)m(TiCl4)n. Titanium dichloride was oxidized by triethylantimony dichloride to give a complex of tervalent titanium, SbEt3·nTiCl3. Triethylstibine reduced titanium tetrachloride and formed an adduct of tervalent titanium, SbEt3Cl2·2TiCl3, when an excess of titanium tetrachloride was allowed to react. An excess of triethylstibine gave rise to complicated reactions with titanium tetrachloride, and formed TiCl3·mSbEt3Cl2·nSbt3 complexes.