A simple sol−gel route has been developed for the preparation of mesoporous and nanocrystalline anatase thin layers. An anatase hydrosol was first synthesized at room temperature from acidic hydrolysis of titanium isopropoxide. The optimization of the synthesis parameters, including titanium concentration, HCl/Ti and H2O/Ti ratios, temperature, and aging time, enabled us to produce a clear sol with a very low HCl/Ti ratio (equal to 1). As a function of the further thermal treatment conditions, it was then possible to control the size of the anatase crystallites (from 5 to >10 nm) and the O/Ti stoichiometry (from 1.9 to 2.0). Ordered mesoporosity was obtained by using a triblock copolymer as the templating agent. Preliminary experiments evidenced the photocatalytic activity of the prepared layers.