Some dry and wet grinding experiments have been respectively conducted on titanium dioxide which is a noble photocatalyst material in a mortar, a tumbling mill and a planetary mill. Anatase is apt to transform to rutile via a metastable phase brookite in every kind of mills in the case of dry grinding. And it hardly takes place for phase transformation from rutile to other forms. It is shown that the kind of mill has not decisive effect on the mechanochemical polymorphic transformation of titanium dioxide, which merely influences the rate of phase transformation. On the other hand, the addition of other liquid media, such as water and acetone, is helpless for phase transformation of anatase. Only anatase can transform to metastable phase brookite by wet grinding. When ground titanium dioxide is heated, the amorphous phase is easier to transform to rutile than metastable phase brookite at lower temperature.