The direct reaction of titanium(IV) oxide dichloride with a range of ligand molecules leads to the formation of complexes of stoicheiometry TiOCl₂,2L, (L = methyl cyanide, trimethylamine, tetrahydropyran, and tetrahydrofuran). With pyridine (py), ethylene glycol dimethyl ether (EGDE), and 1,4-dioxan the following complexes were obtained: TiOCl₂,2·5py, TiOCl₂,EGDE, and TiOCl₂, 1·5C₄H₈O₂. The latter complex can be used as a synthetic intermediate and its reaction with 2,2′-bipyridyl (bipy) and α-picoline (α-pic) results in the displacement of 1,4-dioxan and the formation of TiOCl₂,bipy and TiOCl₂,2α-pic. Only in the case of TiOCl₂,2α-pic and TiOCl₂,2NMe₃ do i.r. spectral measurements indicate the presence of terminal TiO groups. The trimethylamine adduct is shown to be isostructural with its five-co-ordinate vanadium(IV) analogue. The probable structures of the other complexes are also discussed. Detailed electronic spectral measurements are reported for the TiOCl₄^2– and TiOCl₅^3– anions and the absorption bands assigned to transitions of the type halogen(π)→ Ti.