Dopamine, a crucial catecholamine neurotransmitter, plays essential roles in the operation of the central nervous system in humans. Disrupted dopamine release is associated with neurological disorders and depression, therefore monitoring of dopamine levels is imperative for preliminary disease detection. Development of sensitive and selective sensors for neurotransmitters that function under aqueous conditions is however still challenging, mostly due to the complexity of hybrid nanomaterials that are interacting with the electrode. Here we provide a coordination compound constructed from simple substrates, where subcomponent self-assembly leads to a unique, discrete [4 × 4] saddle-type complex [Cu₄(L-H)₄(BF₄)₂(MeOH)₂](BF₄)₂, which was characterized by ESI-MS and FT-IR techniques, including single crystal X-ray diffraction. The Cu₄L₄ complex was subsequently used for modification of the bare Au electrode based on its accumulation on the electrode surface. The new voltammetric sensor (Au/complex) was applied for dopamine detection alone and in the presence of interfering ascorbic acid by using the Differential Pulse Voltammetry (DPV) techniques under aqueous conditions. In the linear dynamic range (LDR) range from 0.0001 mM to 0.75 mM the dependence of the peak current on dopamine concentration satisfied the following linear regression equation: i_p [mA] = 17∙10⁻² c_DA [mM] + 8∙10⁻² (R² = 0.998). Moreover, the excellent limit of dopamine detection (LOD) and the limit of its quantification (LOQ) were established at the level of 5.4 nM and 18.0 nM with accomplished high sensitivity 0.17 A M⁻¹, repeatability as well as reproducibility. Clear separation of the voltammetric signal of dopamine from this one of ascorbic acid, even in the presence of a 100-fold excess of interfering ions found in water, consequently proves that the new prepared sensor can be used as an excellent analytical tool for selective detection of dopamine and ascorbic acid coexisting in the tested samples.