The synthesis, characterization, and computational analysis of Tl(I) complexes bearing the bis(imino)pyridine scaffold, [{ArN=CPh}(2)(NC5H3)]Tl+(OTf)(-) (Ar = 2,6-Et2C6H3 3, 2,5-(Bu2C6H3)-Bu-t, 4), are reported. The cations of these species showed long Tl-N and Tl-OTf distances indicating only weak or no ligand coordination. Computational analysis of the interactions between the Tl cation and the ligands (orbital populations, bond order, and energy decomposition analysis) point to only minimal covalent interactions of the cation with the ligands. The weak ligand-to-metal donation allows for additional interactions between the Tl cation and arene rings that are either intramolecular, in the case of 3, or intermolecular. From benzene or toluene, 4 crystallizes with inverted sandwich structures having two [{(2,5-(Bu2C6H3)-Bu-t)N=CPh}(2)(NC5H3)]Tl+ cations bridged by either benzene or toluene. A density functional computational description of these Tl-arene contacts required exchange-correlation functionals with long-range exchange corrections (e.g., CAM-B3LYP or LC-PBE) and show that Tl-arene contacts are stabilized by noncovalent interactions.