Copper is an essential nutrient for all living organisms, and its deficiency or high levels can have detrimental effects on health. On the other hand, as a heavy metal, it is a highly toxic environmental pollutant. Consequently, it is essential to develop a selective and simple sensor for Cu2+ detection. Here, the electrochemical sensor was designed through the glassy carbon electrode (GCE) modification based on electropolymerization of α-Cyclodextrin (Pα-CD) to detect copper (II) ions. The modified GCE was characterized through field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and differential pulse anodic stripping voltammetry (DPASV), by these methods was exhibited that the conductive polymer (Pα-CD) is coating the GCE surface. The two linear ranges were provided for Cu2+ from 0.004 to 5 nM and 5 to 1100 nM with detection limit (LOD) of 0.0013 nM. The introduced electrode displayed the capability for the selective detection of Cu2+ in the presence of different ions. Moreover, the sensor was successfully employed to detect Cu2+ in soil and water samples. The validation was carried out through cold vapor atomic absorption spectrometry (CVAAS) to detect the Cu2+ in the real samples.