Ordered porous alumina (OPA) with large-scale circular and hexagonal pores was fabricated via etidronic acid anodizing. High-purity aluminum plates were anodized in 0.2-4.2 M etidronic acid solution at 145-310 V and 288-323 K. Self-ordering of porous alumina was observed at 165 V and 313 K in 4.2 M, at 205 V and 303 K in 1.0 M, and at 260 V and 298 K in 0.2 M, and the cell diameter was measured to be 400-640 nm. The ordering potential difference decreased with the electrolyte concentration increasing. OPA without an intercrossing nanostructure could be fabricated on a nanostructured aluminum surface via two-step anodizing. Subsequent pore-widening in etidronic acid solution caused the circular dissolution of anodic oxide and the expansion of pore diameters to 470 nm. The shape of the pores was subsequently changed to a hexagon from a circle via long-term pore-widening, and a honeycomb structure with narrow alumina walls and hexagonal pores measuring 590 nm in its long-axis was formed in the porous alumina. Transition of the nanostructure configuration during pore-widening corresponded to differences in the incorporated phosphorus distribution originating from the etidronic acid anions. (C) 2016 Elsevier Ltd. All rights reserved.