Geometrical, chemical, optical and ionic transport changes associated with ALD of TiO 2 -coating on the porous structure of two nanoporous alumina membranes (NPAMs), which were obtained by the two-step aluminum anodization method but with different pore size and porosity, are presented. Chemical and morphological changes were determined by analyzing XPS spectra and SEM images, showing practically total coverage of the NPAMs surface and leading to a reduction in the geometrical parameters of both samples, while SAED and high resolution TEM measurements allowed us to determine the crystalline structure and thickness of the TiO 2 -coating, with the latter confirmed by depth-profile XPS analysis. Spectroscopic ellipsometry measurements were also carried out in order to detect changes in characteristic optical parameters (refractive index, n, and extinction coefficient, k), due to the TiO 2 -coating of NPAMs. Considering the common application of NPAMs in solute/ion diffusion processes, the effect of the TiO 2 -coverage on electrochemical parameters was analyzed by measuring the concentration potential with a typical model electrolyte (KCl solutions), leading to an increase of the electropositive character for both kinds of samples.