In the present work, well ordered nanoporous anodic aluminum oxides (AAO) have been prepared on aluminum by a two step anodization process in 0.5 M oxalic acid at various potentials. We report the properties and semiconducting characteristics of the porous alumina barrier layers by electrochemical impedance spectroscopy analysis (EIS). EIS is considered to be a highly sensitive and non-destructive technique that allows determining barrier oxide layer characteristics. Aluminum oxide barrier is considered as a semiconductor which acts as a p-n heterojunction at anodizing voltages up to 20 V. The alumina barrier layer structure consists of a hole transport inner layer and an electron transport outer layer. Doping densities, flatband potential as well as space charge layer thickness are discussed in correlation with anodizing potential. Barrier layer thicknesses measurements obtained by EIS were compared with those obtained after EIS measurements by direct scanning electron microscopy observations. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.068208jes] All rights reserved.