The location and coordination of titanium in the titanosilicate mesoporous molecular sieve MCM-41 prepared from Ti(IV) ethoxide as the source of titanium was studied by XRD, IR spectroscopy, Si-29 MAS NMR, and XANES. The results are interpreted on the basis of isomorphous substitution of Ti for Si. XANES shows that titanium is 4-coordinate and that Ti(IV) does not form a regular TiO4 tetrahedron. This is caused by the larger size of the Ti(IV) atom in comparison with Si(IV), resulting in a distortion in the silica matrix, and/or by the presence of H2O in the coordination sphere of titanium. Such distortion is consistent with the line broadening observed in the Si-29 MAS NMR spectra, brought about by the wider distribution of the Si-O-Si angles in SiO4 tetrahedra as titanium is progressively incorporated in the silica matrix, and with the changes in the vibrational lattice infrared bands.