Chlorpromazine (CPZ), an antipsychotic drug derived from phenothiazine, can cause a range of adverse effects in humans, notably visual problems and hematological disorders upon consumption of chlorpromazine‐contaminated water. In this regard, a novel electrochemical sensing platform based on a copper–aluminum‐layered double hydroxide (Cu–Al LDH)‐modified platinum electrode for the highly sensitive and selective detection of chlorpromazine in groundwater samples has been developed. The immobilized Cu–Al LDH showed an electrocatalytic effect on chlorpromazine reduction and oxidation. Among the employed electroanalytical techniques, only the square‐wave voltammetry‐assisted Pt/Cu–Al LDH electrode could detect chlorpromazine with a remarkable sensitivity of 0.065 µA µM−1 over a broad linear detection range of 0.01–760 µM, with low detection and quantification limits of 4.86 and 16.18 nM, respectively. Furthermore, the developed electrode can rapidly detect chlorpromazine within less than 10 s. In addition, the diffusion profiles of steady‐state concentrations of oxidized and reduced chlorpromazine within the immobilized Cu–Al were studied using the Legendre wavelet method. Moreover, the developed Pt/Cu–Al LDH electrode demonstrated satisfactory rates in the quantification of chlorpromazine in groundwater samples, yielding satisfactory recovery rates (97.63–102.57%), confirming the practicability of the fabricated electrode in real‐time monitoring of chlorpromazine levels in groundwater without requiring any sample pretreatment.