Compounds of the general formula MCu(2n)X(n+1), where M is a monovalent metal and X is a chalcogen, exhibit relatively high conductivity and an interesting structural pattern of copper-chalcogen layers. The electronic structure of a series of copper-sulfur layers with the Cu2nSn+1 stoichiometry was studied using the extended Huckel method. Attention was focused on the unoccupied states at the top of the valence band. These states are Cu-S and Cu-Cu antibonding, which accounts for the observed contraction in the plane of the layers. The same states turn out to be strongly delocalized in the plane of the layers, with both copper and sulfur contribution; high mobility of holes in these states is responsible for the substantial conductivity observed in the corresponding materials. The idea of isodesmic reactions, borrowed from computational organic chemistry, was developed to address the relative stabilities of the copper-sulfur layers. We found the Cu2S2- layer to be less stable than the Cu4S3- layer, in accord with experiment.