Adaptive chemistry allows transformation and selection within molecular networks, and adaptive systems composed of different types of dynamic covalent reactions (DCRs) are challenging. Herein, we demonstrate dual reactivity-based covalent networks encompassing the regulation of and switching between C-N- and C-S-based reversible covalent assemblies. The creation and exchange of C-N- or C-S-derived assemblies exhibiting diverse architectures, including linear structures, macrocycles, and cages, were achieved. The shift of reactivity then permitted the interconversion between C-N- and C-S-containing assemblies. Moreover, the adaption of intramolecular and intermolecular scaffolds was feasible via linker design. The latent hemiaminal chirality center offered a pathway for the induction of chirality within assemblies. Finally, switchable structural change and controlled extraction of ions were realized with Hg2+ as a guest for macrocycles. The remarkable complexity of networks described herein could open the door for the utility in sophisticated functional systems.