Over the past decades, numerous efforts have been devoted to synthesizing nanostructured materials with specific morphology because their size and shape play an important role in determining their functions. Self-assembly using weak and reversible interactions or bonds has provided synthetic routes toward various nanostructures because it allows a “self-checking” and “self-error-correcting” process under thermodynamic control. By contrast, the use of irreversible covalent bonds, despite the potential to generate more robust structures, has been disfavored in the synthesis of well-defined nanomaterials largely due to the lack of such self-error-correcting mechanisms. To date, the use of irreversible bonds is largely limited to covalent fixation of preorganized building blocks on a template, which, though capable of producing shape-persistent and robust nanostructured materials, often requires a laborious and time-consuming multistep processes. Constructing well-defined nanostructures by self-assembly using irreversible covalent bonds without help of templates or preorganization of components remains a challenge.