Titanium dioxide (TiO2) is widely used for applications in heterogeneous photocatalysis. We prepared nanocrystalline powders of the anatase as well as the rutile modification by high-energy ball milling of the coarse grained source materials for up to 4 h. The resulting average grain size was about 20 nm. The morphology of the powders was investigated with transmission electron microscopy, X-ray powder diffraction, and BET surface area determination. Measurements of the catalytic activity reveal a maximum as a function of the milling time at about 40 min. This maximum could be explained by a superposition of two counteracting effects. The first one is the increase of the specific surface area resulting in an increase of the catalytic activity, and the second one is a change of the electronic structure at the surface of the TiO2 particles corresponding to a reduction of the surface. The latter one was confirmed by light absorption experiments, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectroscopy.