The application of photocatalytic processes for the decontamination treatment of polluted water has inspired very extensive studies. Titanium dioxide with its large band gap energy and appropriate redox potential was found as one of the most promising semiconductors for the photodegradation of pollutants in the water as well as in gas phase. The titania-silica aerogels obtained by a simple co-hydrolysis method was applied in the photodegradation of the model organic compound. Different ageing times and heat treatment temperatures were found to influence both the activity and the textural properties of the photocatalysts. The obtained aerogels are efficient photodegradation catalysts of methylene blue and allow a removal up to 98 and 78% of the model pollutant from 20 and 500 ppm solutions, respectively.