The environmentally benign route of the organic free process was evolved in precipitating hydrated titania from titanium oxysulphate solution at 90 °C, using crystal nuclei with the addition of ammonia. The synthesized hydrated titania was found to be mesoporous and reactive, with a BET surface area of 277 m2/g. The hydrated titania on calcination in air at 500 °C for 2 h produced anatase mesoporous titania with a surface area of 100 m 2/g. The as-synthesized and calcined mesoporous titania materials were characterized by X-ray diffraction, scanning electron microscopy-energy dispersive X-ray spectrometry, ultraviolet-visible/diffuse reflectance spectroscopy, inductively coupled plasma mass spectrometry, thermogravimetry differential thermal analysis, diffuse reflectance infrared Fourier transform spectrometry, and nitrogen adsorption-desorption measurements. The incorporation of phosphorus in the titania framework was found to inhibit crystallization and particle growth and was found to enhance thermal stability due to the formation of titanyl phosphate. The phosphate-modified hydrated titania exhibited mesopores with a high surface area (172 m2/g) after calcining at 500 °C. The esterification reaction performed on P-TiO2 samples showed the significance of an optimum quantity of anatase phase and phosphate content for catalytic activity. © 2009 American Chemical Society.