Two types of titanium dioxide samples precipitated from aqueous solutions of titanium tetrachloride are investigated. Crystalline materials are obtained by means of neutralization of TiCl4 with the solution of an alkali metal hydroxide. The change of the order of mixing leads to amorphous materials. The evolution of the samples upon the thermal treatment is characterized using XRD, SEM, TEM and porosity studies. The application of crystalline TiO2 as an electrode material in lithium-ion 2016 sample cells enable one to yield specific currents up to 3350mAg−1. On the other hand, the thermal treatment of initially amorphous materials does not lead to complete crystallization, and the presence of amorphous TiO2 is well seen as the so-called capacity behavior of cyclic voltammetry curves.