A solid-contact potentiometric sensor has been developed on the basis of glassy carbon electrode covered with electropolymerized polyaniline and alternatively layered pillar[6]arene and Cu2+ ions films. The assembly of the surface layer was confirmed by surface plasmon resonance measurements. The number of deposited layers was selected to reach better analytical characteristics for Cu2+ determination. It was shown that better results were achieved by using five layers, the upper one consisting of the macrocycle. The addition of covering layers for polyelectrolytes (Nafion, poly(styrene sulfonate)) and Cu2+ ions did not improve sensor performance. The potentiometric sensor made it possible to determine Cu2+ ions in neutral and weakly acidic media with a linear range of the concentrations, from 3.0 mu M to 10.0 mM (limit of detection 3.0 mu M). The applicability of the sensor in real sample assays was confirmed by the determination of Cu2+ ions in copper vitriol, Bordeaux mixture, and polyvitamin-mineral pills of "Complivit" during an atomic emission spectroscopy analysis.