The design of complex supramolecular architectures from simple inorganic components remains a central challenge in nanoscience. Here, we report the hierarchical self-assembly of Gold–Penicillamine (Au-pen) complexes into spiked, hedgehog-like supraparticles. These assemblies arise from controlled coordination between gold ions and the ligand penicillamine, which introduces both steric and chiral constraints during particle growth. The resulting structures exhibit high anisotropy and multiscale organization, reminiscent of biomineralized composites, despite being formed from polydisperse precursors. Morphological complexity was analyzed through electron microscopy and image-based structural mapping, revealing a network of interconnected domains influenced by the balance of thiolate–gold binding, hydrophobic interactions, and steric hindrance. Our findings highlight how subtle variations in ligand geometry and redox-active coordination chemistry can guide the emergence of shape complexity and surface roughness at the nanoscale. These Au-pen hedgehogs represent a new class of supramolecular particles with potential for chiroptical sensing, redox-responsive behavior, and tunable surface interactions in electrochemical or biomedical applications.
