The present work contains the results of structural and electrooptical investigations of potassium caprylate lyotropic liquid crystals doped with viologens. It was proved that electrochromic properties of viologens are preserved after their solution in the liquid crystalline matrix. The samples are colored under the action of an electric field, and relevant features appear in electronic absorption spectra. It is possible to distinguish two stages of the processes that occur in samples exposed to the electric field. The first stage involves the formation of blue-colored radical cations, the second stage corresponds to the dimerization of radical cations and to the red coloring. Data received from the small-angle X-ray scattering showed a presence of the Smectic ordering in the investigated samples and allowed to determine its main parameters. It was inferred that viologen molecules, when present in low concentrations (1–4%), are organically incorporated into the liquid crystal matrix.