A novel potentiometric sensor based on screen‐printed carbon electrode covered with electropolymerized polyaniline (PANI) and unsubstituted pillar[5]arene as ionophore has been developed and tested in potentiometric measurements of pH and metal ions. The introduction of pillar[5]arene improved the reversibility of the pH response in the range from 2.0 to 9.0 with the slope of 45 mV/pH. Among metal cations, the response to Fe3+ and Ag+ ions was referred to PANI redox conversion whereas the signal toward Cu2+ in the range from 1.0×10−6 to 1.0×10−2 M (limit of detection (LOD) 3.0×10−7 M) to specific interaction with the macrocycle.