Assembling micro-/nanostructured arrays on conducting substrates allows the integration of multiple functionalities into modern electronic devices. Herein, a novel self-sustained cycle of hydrolysis and etching (SCHE) is exploited to selectively synthesize an extensive series of metal oxide micro-/nanostructured arrays on a wide range of metal substrates, establishing the generality and efficacy of the strategy. To demonstrate the potential application of this method, the as-prepared NiO porous nanobelt array was directly used as the anode for lithium-ion batteries, exhibiting excellent capacity and rate capability. Conclusively, the SCHE strategy offers a systematic approach to design metal oxide micro-/nanostructured arrays on metal substrates, which are valuable not only for lithium-ion batteries but also for other energy conversion and storage systems and electronic devices at large. [ABSTRACT FROM AUTHOR]