Stimulated by recent reports on quasi-metallicity of colloidal superlattices, we have designed an ad hoc computational approach to investigate the conductive behavior of colloidal crystals of TMA-functionalized NPs held together by mediating CIT ions (Figure ), with the main aim of investigating whether these materials exhibit conductivity behavior typical of metals, semiconductors, or insulators. We investigated these specific colloidal crystals as a representative case of larger NPs that arrange into an ordered FCC lattice (AAs) surrounded by a large number of smaller counterions (EAs) that can move in the supercrystal. We use a CG molecular model of FCC lattice that, while approximated, allows studying the lattice in its complexity and retains the essential physical features of the system, providing us with fundamental indications on the behavior of such materials (Figure ). By studying the behavior of the superlattice under the influence of an external electrostatic field, we obtain data explicitly demonstating how these TMA-NP crystals possess a supramolecular semiconductive character, which allows conduction of CIT ions as charge carriers above a threshold activation E intensity (Figure ). In this case, the current is generated by the motion of the CIT ions that, unlike free-electrons in metals, is triggered by and follows classical motion and statistics. Our in silico ohmic experiments show how for weak values of the external field E, no current is generated, but, when the E intensity overcomes a certain threshold value, an ionic density current proportional to the external field is generated in the system (Figure ). We observe a transition from a non-conductive to a conductive regime reminiscent of that of semiconductors, while in such supramolecular systems crossing the "band gap" requires providing a sufficient E intensity to break the electrostatic interaction of the CIT ions with the TMA-NP surface and have free-ions that diffuse in the system (Figure ).