In this study, a new carbon paste electrode modified with a laboratory-synthesized ligand, N1-hydroxy-N1,N2-diphenylbenzamidine (HDPBA) and multi-walled carbon nanotubes (MWCNTs) (HDPBA‒MWCNTs/CPE) has been developed. The modified electrode was applied for preconcentration and voltammetric determination of zinc ions (Zn(II)) by square wave anodic stripping voltammetry (SWASV). The preconcentration of Zn(II) on the electrode surface was performed in 0.1 M Brinton Robinson (B–R) buffer solution (pH 6) at an applied potential of −1.30 V versus Ag/AgCl for 120 s, followed by stripping in the positive potential scan of the SWASV after a quit time of 10 s. Under optimized experimental conditions, the proposed electrode exhibited a wider linear dynamic response for Zn(II) in a concentration range of 0.02–10.00 μM with a detection limit of 2.48 nM. This is due to the excellent metal-chelation property of the ligand, and the good conductivity and large surface area of MWCNTs which significantly improved the sensing performance of the nanocomposite modified electrode. The selectivity of the electrode was studied by evaluating the interference effects of various foreign ions on the peak current of Zn(II). The method exhibited high reproducibility with a relative standard deviation (RSD) of 3.1%. The present method was applied for the determination of zinc ions in water samples. The recovery values in the tested samples were found to be 98.50–106.0%, indicating a good accuracy of the proposed electrode. Furthermore, the electrochemical behavior of HDPBA in acetonitrile and aqueous solutions has been studied.