The band structures of 11 one-dimensional (ID) poly-decker sandwich compounds with different transition metal centers M (M = Mn, Fe, Co, Ni, Cu, Zn) and a variety of fivemembered π ligands L from the cyclopentadienyl moiety (C 5 H 5 ) to the pure boron ring B 5 H 5 have been studied by means of a semiempirical crystal orbital procedure based on the INDO approximation in order to allow a priori predictions on possible semiconducting or conducting low-dimensional materials composed by ML fragments. To determine the (numerically) different selfenergy corrections (i.e. long-range and short-range “correlations”) in the transition metal 3d spines and the ligand backbones approximate quasi-particle shifts have been employed for the correction of the Hartree-Fock (HF) band energies. The band structure properties (e.g., dispersion curves, density of states distributions, effective mass parameters, propagation times of charge carriers) are discussed in the light of the semiempirical tight-binding approach. It is shown that the forbidden band gaps are reduced with an increasing number of B atoms in the π ligands. The gap in the Mn(C 5 H 5 ) stack amounts to 8.27 eV, while overlapping dispersion curves are predicted in the Zn(B 5 H 5 ) derivative. This model polymer is the only intrinsic conductor in the series of the studied ID metallocenes; all other compounds require injected charge carriers (electrons or holes) in order to achieve partially filled bands. Injected holes in the Mn or Fe backbones lead to ID materials with conducting 3d spines; the charge transfer in this regime is best described as some type of hopping motion. The remaining poly-decker strands belong to the class of organic metals (injected carriers) with conductive pathways that are formed by diffuse ligand states leading to transfer processes that can be rationalized in terms of a band picture. The rotational profiles and the magnitudes of intracell and intercell interactions are also studied. The band structure properties (band gaps, characters of the valence and conduction bands) depend critically on the mutual orientations between neighbouring unit cells in the case of ligands with low spatial symmetries. General rules and strategies for synthetic approaches to organometallic ID materials containing 3d centers with small or vanishing band gaps are formulated.