Nanocrystalline powders of TiO2 xerogel and aerogel were prepared by using acid-modified sol–gel approach. For TiO2 aerogel material (TA), the solvent was high temperature supercritically extracted at 300 °C and 100 bars. However, the TiO2 xerogel material (TX) was dried at 200 °C and ambient pressure. The effects of the drying processes on the crystalline structure, phase transformation and grain growth were determined by Raman spectroscopy, SAED and X-ray diffraction (XRD) analyses using Rietveld refinement method. The TiO2 aerogel was composed of anatase crystalline structure. The TiO2 xerogel material was composed of anatase, brookite and small amount of amorphous phase with anatase as dominant phase. The TX sample still contains a relatively high concentration of carbon than that of TA, indicating the amorphous character of TiO2 xerogel. These materials were applied as catalyst for the degradation of indigo carmine in aqueous medium. Photo-degradation ability of TA and TX was compared to the TiO2 commercial Degussa P25. The photo-catalytic results showed that the degradation efficiency was in the order TA > P25 > TX. The photo-degradation of indigo carmine followed pseudo first order reaction kinetics. Keywords: Sol–gel, Xerogel, Aerogel, Supercritical drying, Photodegradation