Among the toxic metals, cadmium is a very dangerous pollutant because it can extremely damage organs in humans and animals. This toxic metal is introduced into water from different industries such as metal plating, batteries, and alloys. Cadmium bioaccumulates in vital organs and unlike organic pollutants does not show any biological degradation. In this study, an electroactive self-assembled monolayer (SAM) was developed by covalent attachment of a novel mono aza-crown ether substituted catechol-terminated hexane dithiol onto the gold surface. The electrochemical behavior of the fabricated SAM electrode was investigated using voltammetry techniques and electrochemical impedance spectroscopy (EIS). The obtained results from voltammetric experiments revealed that the crown ether moiety of SAM forms a selective complex with cadmium ion. Under optimal conditions, Cd2+ could be detected in the range of 15 μM to 65 μM with a detection limit of 4.5 μM. Selectivity measurements reveal that the sensor is specific for Cd2+ even in the presence of high concentrations of other metal ions. The proposed sensor was applied to the determination of cadmium ion in water samples with high sensitivity and good selectivity.