Pioneering works have shown how the selectivity of DNA interactions can be exploited to assemble NPs functionalized with single-stranded DNA into a variety of superstructures with symmetries typical of a metallic crystal. As "atom equivalents", the NPs in such supercrystals are surrounded by the smaller particles, which keep them together as superelectron equivalents. Experiments and molecular simulations showed how the electron equivalents can break their distribution symmetry around the atom equivalents and move in the superlattice in a way resembling the behavior of electrons in metals. Similar intra-lattice mobility has also been observed in aggregates of gold NPs decorated with a high density of positively charged groups. Cl -counterions coassembled with NP decorated with a high-density of (11-mercaptoundecyl)-N,N,N -trimethylammonium (TMA) groups, generating colloidal superclusters with semiconductive properties useful to build chemoelectronic circuits. More recently, static and dynamic superlattices have been also obtained via mediated assembly of TMA-NPs (atom analogs, AAs) in water using citrate (CIT) or ATP as counterions. Also in this case, a rich dynamics of the CIT ions (behaving as electron analogs, EAs) was observed in the TMA-NP superlattices. While the ability of the EAs to move in AA superlattices may suggest intriguing hierarchical analogies with atomic crys-talline materials, the behavior of metals and semiconductors present specific fingerprints, whose presence is non-trivial to ascertain in higher-scale supercrystals.