Some new complexes of compositions have been isolated from the reaction of titanium tetrachloride (TiCl4) with dialkyl/diaryl phosphites in different molar ratios and under varying condition of temperature and solvent. The complexes have been characterized on the basis of elemental analysis, infrared spectral data and magnetic susceptibility measurement. The lowering of the frequency in the spectra of complexes is indicative of octahedral environment around the central of Titanium metal ion and of the polymeric nature of complexes.