Structure, stability, and electronic properties of the bimetallic {[IrI(terpy)(Me)]-[BiIIINNN]}n monomeric, oligomeric, and polymeric structures (n = 1-3 and ∞; terpy = terpyridine; Me = methyl; BiNNN = bismuth triamide) and their derivatives (designated as (Bi·Ir)n structures) were studied theoretically by DFT cluster and periodic calculations. Stable Bi·Ir adducts (monomers) were formed with short Bi-Ir bonds (<2.7 Å) and Gibbs free binding energies larger than 20 kcal/mol for all systems. The substitution of the pincer ligands of Ir(I) and Bi(III) complexes by the electron-donating (NH2) and electron-withdrawing (NO2, F, CF3) groups, respectively, enhanced the Ir → Bi charge transfer, substantially stabilizing the Bi·Ir monomers. The monomers from the unsubstituted complexes can be considered as dispersion stabilized adducts, and they may form spontaneously (Bi·Ir)n layered oligomers/polymers with semiconducting properties. The self-assembly of monomers into oligomers/polymers is hindered by bulkier protecting groups on the Bi(III) complex, such as tBu and SiMe3.