Intricate hollow transition‐metal oxides (TMOs)‐based hetero‐nanostructures demonstrate intriguing applications in electronics, energy storage, and catalysis owing to their exotic electronic features and geometric complexity; however, manipulating their topological features and interfacial interactions of different subunits, is a grand challenge because most TMOs are intrinsic non‐layered crystals. Herein, a generalized multidentate ligand chelating‐grafting strategy for creating various amorphous TMOs‐based triple‐layered hetero‐nanotubes with face‐to‐face contact is demonstrated, by taking ethylenediamine tetraacetic acid (EDTA) chelating agent and melamine‐cyanuric acid (M‐CA) supramolecular complex‐polymer as a proof‐of‐concept. This strategy primarily depends on controlling the chelation of coordinated covalent bonds and grafting of hydrogen bonds, in which EDTA is utilized to chelate metal ions, and subsequently grafted to M‐CA supramolecular surface, followed by annealing treatment. Merited by the optimized structure in three natures of nanotubes‐interface‐heterolayers, the obtained hollow nanostructure possesses superior photocatalytic performance: the optimized a‐ZnO/C/CN hetero‐nanotube exhibits high hydrogen evolution rate of 400.01 μmol h−1 g−1, outperforming the bulk CN by about 14.29‐fold. The synthesis of various a‐TMOs‐based complex hollow nanostructures and the demonstration of high catalytic activity are expected to enable fundamental studies of cavity, hereto‐interface, and dimensionality effects on their properties and facilitate their use in catalysis and other applications.