Because −NH2 and −NH− in poly-[Formula: see text]-phenylenediamine (P[Formula: see text]PD) can interact strongly with the empty orbitals of Cu to show unique electrochemical activity, P[Formula: see text]PD is suitable for the removal of Cu[Formula: see text] by electrochemical oxidation–reduction process. In this study, with P[Formula: see text]PD and its carbon dot composite (CDs/P[Formula: see text]PD) as working electrodes, the electrochemical reduction and removal of Cu[Formula: see text] in the aqueous solution were carried out with the potentiostatic method. According to effects of voltage, pH of the solution, initial concentration of Cu[Formula: see text], and electrochemical reduction time on the Cu[Formula: see text] removal, the Cu[Formula: see text] removal ratios of P[Formula: see text]PD and CDs/P[Formula: see text]PD were up to 64.69% and 73.34%, respectively, at −0.2 V and the optimal pH. Additionally, results showed that these processes were in line with the quasi-first order kinetic model. Both P[Formula: see text]PD and CDs/P[Formula: see text]PD showed good reproducibility in six cycles. After five times of repeated usage, the regeneration efficiencies of P[Formula: see text]PD and CDs/P[Formula: see text]PD dropped to 77.04% and 79.36%, respectively.