Achieving synthetic architectures with simple structures and robust biomimetic catalytic activities remains a great challenge. Herein, we explore a facile supramolecular assembly approach to construct a dipeptide-based hierarchical nanoarchitecture with enhanced enzyme-like catalytic activity. In this nanoarchitecture, nanospheres are with chain-like arrangement through coordination-driven directional self-assembly. The reversible transformation of anisotropic nanochains to isotropic nanospheres switches biomimetic activity. Notably, such assembled nanoarchitecture exhibits high enzyme-like activity and remarkable long-term stability to promote hydroquinone oxidation, superior to the natural counterpart. This work will pave the way to develop reversible and reusable supramolecular biocatalysts with ordered hierarchical structures for accelerating chemical transformations.