AbstractThe noncovalent interactions between a redox‐active molecule, phenyl‐substituted 1,4‐dithiafulvene (Ph‐DTF), and ten commonly encountered nitroaromatic compounds (NACs) were systematically investigated by means of density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. Our modeling studies examined their 1:1 complexes in terms of equilibrium geometries, frontier molecular orbitals (FMOs), nature of noncovalent forces, intermolecular charge transfer (ICT), and interaction energies at the ωB97XD/6‐31+G(d,p) level of theory. Vertical electronic transition properties were investigated through time‐dependent density functional theory (TD‐DFT) calculations, and energy decomposition analysis was conducted according to the symmetry‐adapted perturbation theory (SAPT). The computational results indicate that Ph‐DTF can form thermodynamically stable 1:1 complexes with trinitro‐substituted benzenes (e.g., 2,4,6‐trinitrotoluene and picric acid), but its interactions with mono‐ and dinitrobenzenes do not exhibit such stability. The selective binding properties are further corroborated by AIMD simulations. Overall, this computational work establishes a comprehensive understanding of the nature of noncovalent interactions of Ph‐DTF with various NACs, and the results can be used as theoretical guidance for the rational design of selective receptors and/or chemosensors for certain NACs that are of great concern in current industrial applications and environmental control.