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Atomic force microscopy (AFM), in particular force spectroscopy, is a powerful tool for understanding the supramolecular structures associated with polymers grafted to surfaces, especially in regimes of low polymer density where different morphological structures are expected. In this study, we utilize force volume mapping to characterize the nanoscale surfaces of Ag nanocubes (AgNCs) grafted with a monolayer of polyethylene glycol (PEG) chains. Spatially resolved force−distance curves taken for a single AgNC were used to map surface properties, such as adhesion energy and deformation. We confirm the presence of surface octopus micelles that are localized on the corners of the AgNC, using force curves to resolve structural differences between the micelle “bodies” and “legs”. Furthermore, we observe unique features of this system including a polymer corona stemming from AgNC−substrate interactions and polymer bridging stemming from particle−particle interactions.