Self-ordered anodic porous alumina with a long-range ordered hole arrangement having an inter-hole spacing of over 1.5 μm was prepared by anodization in a citric acid electrolyte containing a small amount of phosphoric acid. The inter-hole spacing of the ordered anodic porous alumina could be controlled within a range of 700 nm to 1.8 μm by adjusting the anodization conditions. The use of an electrolyte with a mixture of water and ethylene glycols, especially tetraethylene glycol, was effective for preparing ordered anodic porous alumina with large inter-hole spacings. The obtained anodic porous alumina is suitable for various applications that require highly ordered hole array structures with large inter-hole spacings.