The electrochemical behavior of PEDOT/NiO composite films obtained by electrochemical deposition of nickel into poly-3,4-ethylenedioxythiophene (PEDOT) films followed by oxidation in weakly alkaline solutions was studied by cyclic voltammetry. When a complex polymer composite with two sequentially deposited PEDOT/NiO layers was prepared, the charge almost doubled. The morphology of the obtained composite films was studied by scanning electron microscopy (SEM); the element composition was analyzed by local energy dispersion (EDX) analysis. The nickel distribution over the surface was mapped for the PEDOT/Ni and PEDOT/NiO composite films. The specific capacity of the obtained materials and their dependence on the potential scan rate were determined by cyclic voltammetry.