Ion intercalation processes into metal oxide porous materials benefit from a high surface-to-volume ratio, while electronic charge transport requires a continuous network morphology. Detailed control over structure formation on the 10 nm length scale is therefore an effective strategy to enhance performance in electrochromic devices, supercapacitors, and batteries. Here we demonstrate the transformation of nickel patterned in a three-dimensional, highly interconnected, periodic nanomorphology into a self-supporting nickel oxide array with hollow struts. The oxidation of nickel gives rise to the nanoscale Kirkendall effect, which substantially increases the surface area of the NiO gyroid framework, without sacrificing its connectivity. Applicable to a vast range of electroplatable metals, this is a versatile route to high surface area metal oxides/chalcogenides which is especially suitable for various thin film applications. Nanostructured NiO electrodes showed substantially enhanced electrochromic performance, combining fast switching speeds with high coloration contrast.