The coordination chemistry of the homo- and heterodipnictogen tetrahedrane complexes [{CpMo(CO)2}2(μ,η2:2-EE′)] (E, E′ = P, As, Sb) (A–F) toward Tl[BArF24] ([BArF24]− = [B(3,5-C6H3(CF3)2)4]−) was studied. Controlled by the used tetrahedranes A–F, and thus depending on the respective pnictogen atoms, the monomers [Tl(η2-A)][BArF24] ([A]Tl) and [Tl(η2-B)][BArF24] ([B]Tl), the double substituted [Tl(η1-C)2][BArF24] ([C]2Tl) or the even higher aggregated compounds [Tl2(η2-D)3(μ,η2:1-D)(μ,η1:1-D)][BArF24]2 ([D]5Tl2), [Tl2(η2-E)2(μ,η2:1-E)3] [BArF24]2 ([E]5Tl2) and [Tl2(η2-F)3(μ,η2:1-F)3][BArF24]2 ([F]6Tl2) were obtained. Utilization of [BArF24]− promises additional stabilization of TlI via η6-coordination of two of its aryl rings as found in compounds [A]Tl, [B]Tl and [C]2Tl. Within the series of reactivity of A–F, the heavier congeners D, E and F tend to form larger aggregates in which σ(E–E′) bond contributions to the coordination behavior were observed. Interatomic distances suggest the presence of Tl···Tl interactions in [E]5Tl2 and [F]6Tl2. The features of the respective coordination compounds were studied in the solid-state as well as in solution. For the latter at least a partial dissociation of the assemblies in solution was indicated. The isolated solid-state aggregates are the first examples of heterodipnictogen units as ligands in self-assembled TlI-based coordination compounds.