The self-assembly of nanoparticles driven by small molecules or ions may produce colloidal superlattices with properties reminiscent of those of metals or semiconductors. However, to what extent the properties of such supramolecular crystals actually resemble those of atomic materials often remains unclear. Here, we present coarse-grained molecular simulations explicitly demonstrating how a behavior evocative of that of semiconductors may emerge in a colloidal superlattice. As a case study, we focus on gold nanoparticles bearing positively charged groups that self-assemble into FCC crystals via mediation of citrate counterions. In silico ohmic experiments show how the dynamically diverse behavior of the ions in different superlattice domains allows the opening of conductive ionic gates above certain levels of applied electric fields. The observed binary conductive/non-conductive behavior is reminiscent of that of conventional semiconductors; however, at a supramolecular level, crossing the “band-gap” requires a sufficient electrostatic stimulus to break the electrostatic interactions and make ions diffuse throughout the superlattice’s cavities.