An enantioselective voltammetric sensor (EVS) comprising a paste electrode made of graphitized thermal Carboblack C (CBPE) modified with a Ni(II) complex based on (S)-(2-aminomethyl)pyrrolidine and 3,5-di-tert-butylsalicylaldehyde was developed for the recognition and determination of naproxen (Nap) enantiomers. The proposed sensor was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS-SEM), Fourier-transform infrared spectroscopy (FT-IR), molecular dynamics and quantum chemical simulations, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) methods. Using the differential pulse voltammetry (DPV), the CBPE@(S)-Ni sensor was found to have good selectivity for Nap enantiomers (i