We demonstrate the proof of an innovative concept of fabricating nanostructured aluminum oxide cladding on silica optical fiber. Our fabrication strategy entails freeze-coating aluminum on silica fiber and its subsequent anodization, resulting in the formation of anodized aluminum oxide (AAO) cladding with highly organized nanopore channels vertically aligned to the fiber axis. We show that the structure (diameter of pore channels and the porosity) of AAO cladding can be controlled by varying anodization conditions such as the type and concentration of electrolyte solutions and applied voltage. The versatility of AAO as a cladding with tunable structural and optical characteristics and/or a host of other functional nanostructures within the pore channels has the potential to enable a new class of specialty optical fiber for new sensor architecture and applications.