By the method of density functional theory (B3LYP, 6-31G **) the electronic structures of poly 3,4-ethylenedioxythiophene containing 12 links in charge states 0, +1, +2, +3 and +4 were calculated. It is shown that the oligomer of 12 units is sufficient to reflect the properties of the conductive polymer. To estimate the probability of electron density movement along the polymer chain, the width of the energy gap between NOMO and LUMO was calculated. It is shown that the molecules of oligomers EDOT and SS do not remain parallel to each other after polymerization, but rather, with increasing chain length, the latter gradually bends around the anionic unit SS; the charge distribution in the EDOT and SS oligomer complexes indicates the presence of two separated polarons at the two ends of the chain, and the asymmetry in the charge distribution also implies the presence of a curved spiral structure of the formed complex.