The contamination by heavy metals (HMs) is a pressing issue, due to their serious impact on the environment and human health. Therefore, the design and the development of a sensing material for their detection has gained a lot of attention. In this study, active layers are produced by the electrospinning technique, using three different polymers and disodium salt of ethylenediaminetetraacetic acid (Na2‐EDTA), known to be a chelating substance for heavy metals. The optimized active layer, in terms of polymer type, degree of encapsulation of the salt, as well as salt suitable content, is obtained and tested using the electrochemical impedance spectroscopy technique. The results of the sensing tests indicate the suitability of the developed electrospun layer for environmental monitoring. It is shown the detection of lead in the range of 10–100 000 µg L−1, with a detection limit of 0.031 µg L−1. Moreover, the system is proved to be robust against interfering contaminants such as thallium, another relevant heavy metal.