Rapid development of modern society raises more and more requirements for highly efficient energy conversion and storage. Electrochemical devices stand out as a most viable option for eventual substitute for fossil fuels, but suffer from problems like durability, operability, etc. Heterogeneous nanostructure arrays with distinguished superiorities have thus attracted intensive attention and yielded favorable electrochemical performance. In pursuit of deep understandings of their working modes,

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... his review will focus on the interconnection among different constituents within each individual unit to correlate microscopic electrochemical processes with macroscopic performance. Here, the motivation of employing heterogeneous nanostructure arrays is first summarized. Then, the design principles, including three working modes, 'Function-Function', 'Function-Assistance', 'Single-unit device', are analyzed comprehensively to illuminate the interconnection among different constituents in electrochemical energy conversion and storage processes. Solar water splitting (energy conversion), alkali-ion battery and supercapacitors (energy storage) are termed collectively as typical electrochemical energy technologies to illustrate the