The work is devoted to an experimental study of the electrical conductivity along the polymethyl methacrylate/polymethyl methacrylate interface, as well as to the study of the supramolecular organization of a polymer film by the density functional theory method. The influence of the concentration of dipole moments on the conductivity of the polymer/polymer system was also studied. The concentration of dipole groups at the interface between the films was changed by introducing a low molecular weight dopant with a large dipole moment into the polymer matrix. A strong influence of the concentration of dipole groups on the electrical conductivity along the interface has been found. The studies were carried out according to a two-probe scheme by the method of currentvoltage characteristics. The interpretation of the obtained results was carried out within the framework of the injection model of currents limited by the space charge. An assessment was also made of the electrophysical parameters of charge carriers, such as concentration and mobility. An analysis of the results obtained made it possible to assume that a new electronic state of the type of a quasi-two-dimensional electron gas is formed along the PMMA/PMMA interface. Quantum-chemical studies have shown that the most energetically favorable PMMA configurations are linear syndiotactic and helical syndiotactic