EXAFS and XANES spectra of methyl acrylate-TiCl4 complexes in nitrobenzene show that the titanium atom is coordinated to two oxygen atoms and four chlorine atoms for any methyl acrylate/TiCl4 ratio; furthermore, there is no free TiCl4, so some carbonyls must be coordinated to two titanium atoms, as confirmed by IR spectroscopy; coordination increases the titanium-chlorine distance with regard to TiCl4.