The electrical conductivities and plausible charge-ordering states in the room temperature (r.t.) phase for MMX chains [Ni(2)(dta)(4)I](∞) and [Pt(2)(dta)(4)I](∞) (dta = CH(3)CS(2)(-)) have been analyzed with periodic density functional theory (DFT) and correlated ab initio calculations combined with the effective Hamiltonian theory. Periodic DFT calculations show a more delocalized nature of the ground state in [Pt(2)(dta)(4)I](∞) compared to [Ni(2)(dta)(4)I](∞), which features a rather large energy gap between the occupied and empty bands, and charge polarized dimer units. A larger electrical conductivity for the Pt chain can be expected, especially because the Fermi level lies within a band with contributions from Pt and I orbitals. Electronic structure parameters extracted from ab initio cluster calculations show that the large difference between the observed conductivities at 300 K for Ni and Pt compounds, of 3 orders of magnitude, cannot be explained from the parameters extracted from an embedded M(2)(dta)(4)I(2) dimer fragment alone. When tetramer fragments are considered, we observe that the interdimer transfer integral (t) between neighboring M(2) units connected by an iodine atom at correlated level is comparable in both chains. On the other hand, the energy to transfer an electron from a dimer to the neighboring one (Coulomb repulsion U) is three times larger in the Ni compound with respect to the Pt chain, in line with the poor conductivity of the former. The electronic structure of the M(4)(dta)(8)I(3) fragment points to an alternate charge-polarization state for Ni and an average valence state for Pt when the r.t. X-ray structure is considered.