This paper presents the synthesis of the ligand 1picolinoyl-4-cyclohexyl-3-thiosemicarbazide (H 2 pctc) and new metal complexes [Ni(Hpctc) 2 ] (1), [Cu(Hpctc)Cl] (2), and [Cd(Hpctc) 2 ] (3). The synthesized metal complexes were precisely characterized using single crystal X-ray diffraction (SC-XRD). In addition, complexes 1−3 were also characterized by UV−vis, fluorescence, and infrared spectroscopy. SC-XRD data confirmed the distorted octahedral geometry around the Ni(II) and Cd(II) centers and the distorted square planar geometry around the Cu(II) center. Data derived from the emission spectra depict that higher fluorescence intensity was exhibited by complexes 1, 2, and 3 in comparison to that of the free ligand H 2 pctc, and complex 3 showed the maximum intensity. Further, these metal complex-modified GCEs (glassy carbon electrodes) were utilized for electrochemical sensing of dopamine (DPM). The electrochemical studies of these complexes were performed using modified glassy carbon electrodes supported by electrical impedance spectroscopy (EIS) and cyclic voltammetry (CV) methods. In contrast to complexes 1 and 3, complex 2 is a superior electrode material with a high effective surface area for the electrochemical oxidation of DPM, according to the electrochemical response results. The derived sensor had a wide linear detection range of 1 to 1400 μM, an acceptable sensitivity of 0.01531 μA cm −2 μM −1 , and a low LOD of 0.38 μM. The proposed approach was free of the interfering effects of ascorbic acid, uric acid, aminophenol, and other substances. During the successive scans, no fouling of the electrode surface was observed. The proposed electrochemical sensor had excellent stability, sensitivity, and a low detection limit making it suitable for the analysis of a variety of real samples. Additionally, it was proven to be useful for analyzing biological fluids.