Two titanium phosphate materials (TpP and ThP) have been successfully synthesized by sol-gel route with controlled precipitation and hydrolysis. The TpP material was obtained from the reaction between precipitated titania and phosphate buffer solution H2PO4−/HPO42−(pH = 7.3). The TpP material was prepared through hydrolysis of titanium in the presence of H2PO4−/HPO42. The probable state of the phosphate anions in titania framework and their effect on the anatase-to-rutile transformation were characterized by ICP-AES, DTA-TG, 31P NMR, FT-IR, and Raman analysis HRTEM/SEM. FT-IR and 31P NMR analyses of titanium phosphate TpP calcined at low temperature showed that the phosphate species existed not only as Ti-O-P in the bulk TiO2but also as amorphous titanium phosphates, including bidentate Ti(HPO4)2and monodentate Ti(H2PO4)4. Increased calcination temperature only gave an enrichment of bidentate structure on the titania surface. For the TpP material, H2PO4−/HPO42−anions were introduced into the initial solution, before precipitation, what promoted their lattice localization. At high temperatures, all the phosphorus inside the bulk of TiO2migrated to the surface. The Raman analysis of both samples showed that the bidentate phosphates increased the temperature of the anatase-to-rutile phase transformation to more than 1000 °C with the formation of well crystalline TiP2O7phase. This phenomenon was more evident for TpP sample.