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Constructing multi-dimensional hierarchical superstructures has been, for a longtime, regarded as a promising strategy for modifying the physiochemical properties of nanomaterials. Guided by this rule, this work reports the synthesis of hierarchical superstructures of Ag-Ag₂O-AgO nanoparticles (HSANs) using a convenient and surfactant-less photochemical method under 254 nm UV-irradiation. The formation of the HSANs superstructures is dominated by screw-dislocation-driven growth mechanism at low supersaturation condition. The structural evolution of the HSANs superstructures has been systematically investigated. The average size of the HSANs superstructures increased with prolonged 254 nm UV-irradiation. The step density on the superstructure surfaces also increased along with the 254 nm UV-irradiation time.