The crystal and molecular structure of dichlorobis-8-quinolinolatotitanium(IV), TiCl2(C9H6NO)2, has been determined by three-dimensional X-ray diffraction. The unit cell is monoclinic with a= 14·06, b= 8·54, c= 14·97 Å, β= 111° and space-group C2/c. The structure was solved by use of 1415 visually estimated intensities by Patterson and Fourier methods and refined by least squares to an R value of 0·116. The structure consists of monomeric units of TiCl2Ox2, with two-fold symmetry, in which the titanium atom is octahedrally co-ordinated by two chlorine atoms in a cis configuration, at a distance of 2·283 Å, two nitrogen atoms also cis at 2·200 Å, and two oxygen atoms in a trans configuration at 1·888 Å. The large difference between the Ti–N and Ti–O distance is discussed and compared with distances in other metal–oxine complexes.