Changes associated to atomic layer deposition (ALD) of SiO2 from 3-aminopropyl triethoxysilane (APTES) and O3, on a nanoporous alumina structure, obtained by two-step electrochemical anodization in oxalic acid electrolyte (Ox sample) are analysed. A reduction of 16% in pore size for the Ox sample, used as support, was determined by SEM analysis after its coverage by a SiO2 layer (Ox+SiO2 sample), independently of APTES or O3 modification (Ox+SiO2/APTES and Ox+SiO2/APTES/O3 samples). Chemical surface modification was determined by X-ray photoelectron spectroscopy (XPS) technique during the different stages of the ALD process, and differences induced at the surface level on the Ox nanoporous alumina substrate seem to affect interfacial effects of both samples when they are in contact with an electrolyte solution according to electrochemical impedance spectroscopy (EIS) measurements, or their refraction index as determined by spectroscopic ellipsometry (SE) technique. However, no substantial differences in properties related to the nanoporous structure of anodic alumina (photoluminescent (PL) character or geometrical parameters) were observed between Ox+SiO2/APTES and Ox+SiO2/APTES/O3 samples.