The atomically resolved structure of layered titanate, H(x)Ti((2-x/4))square(x/4)O(4). H2O, films fixed on various substrates (glass, mica, and gold deposited on mica) was determined by using atomic force microscopy (AFM). Two TiO6 layers deposited as a unit sheet on the mica from a dilute suspension, and the film consisted of an accumulation of these superfine sheets with the b-axis perpendicular to the substrate surface. Electrochemical deposition and dissolution process of the H(x)Ti((2-x/4))square(x/4)O(4). H2O sheets was also investigated by an in situ electrochemical AFM measurement. The presence of some H3O+ ions on the outside of the TiO6 layers as well as in the interlayer was suggested, because the sheets cathodically deposited on the Au electrode.