Thin oxide layers obtained by electrochemical oxidation of titanium were studied using grazing X-ray diffraction (GXRD) and X-ray absorption spectroscopy (XAS). In the precursor state the layers, with thicknesses ranging from 15 to 105 nm, appeared to be amorphous by GXRD whereas a short-range order is detected via XAS with a first O shell and a second Ti shell, rather similar to those of crystallized anatase. Subsequent treatments of the layers such as aging under polarization or thermal annealing led to ordering on a larger scale and to crystallization in the anatase form.