Self-assembled alkyl phosphate layers have been formed on a flat, anodized aluminum substrate in dilute ethanol solution containing 2 wt% n-tetradecylphosphonic acid (TDP) and examined by low-voltage scanning electron microscopy as well as atomic force microscopy and X-ray photoelectron spectroscopy. Locally, multi-layered alkyl phosphate films have been formed on aluminum, being clearly observed by a low-voltage scanning electron microscope operated at less than 1 kV. Atomic force microscopy observations disclosed that bilayers of tetradecylphosphonic acid are stacked on the substrate to form multilayers. The present study revealed that the uniform self-organized monolayer is not always formed readily on an oxidized aluminum surface. Copyright © 2013 John Wiley & Sons, Ltd.