We have measured the photoelectron spectra of the multiple-decker 1:1 sandwich clusters of Eu-n(COT)(n)(-) (n = 1-4; COT = 1,3,5,7-cyclooctatetraene), synthesized in the gas phase, and studied theoretically the bonding scheme, charge distribution, valence orbital energies, and photodetachment energies. We calculated the ground electronic state X- and the first excited electronic state A(-), both of which have strong ionic bonding and a characteristic charge distribution. Moreover, we found that the valence orbital energies of Eu (6s) and COT (L-delta) depend strongly on cluster size and their positions in the clusters. With the calculated vertical detachment energies for these valence orbitals, we assigned the peaks in the experimental photoelectron spectra and analyzed the origin of their interesting behavior by employing simple point charge models. From these analyses, it became clear that the characteristic behavior of the spectra is due to the strong ionic bonding and the charge distribution. In addition, using the point charge models, we estimated the vertical detachment energies of the one-dimensional polymer [Eu(COT)](infinity)(-).