The synthesis of a chiral dinuclear [Cu(OAc)₂(L1)]₂ complex (A) and its analogues Cu(OAc)₂(L1)₂ (B), Cu(OAc)₂(L1)PPh₃ (C), CuBr(L1)PPh₃ (D), and Cu(OAc)₂(L2) (E) is described. The X-ray structure of A reveals a cuprophilic interaction (2.65 Å) and shows that L1 behaves as a monodentate ligand. The stereogenic centre in L1 aligns the NH group to form non-covalent interactions with the paddle-wheel acetate groups at variable distances (2.4–2.5 Å and 2.2–2.7 Å). Thermogravimetric analysis confirmed our hypothesis that two equivalents of L1 (B) or a combination of L1 and PPh₃ (C) would disrupt the cuprophilic interaction. All complexes, except D, showed irreversible redox waves by cyclic voltammetry. Complexes C and E have lower oxidative peaks (at 10 V s⁻¹) than complex A between +0.40 and +0.60 V. This highlights the influence of ligand(s) on the redox behaviour of Cu(II) complexes. The significance of this electrochemical behaviour was evident in the Chan–Lam (CL) coupling reaction, where 2.5 mol% of A successfully facilitated the formation of a C–N bond. This study showcased the structure, thermal stability, electrochemical properties and catalytic performance of a chiral dinuclear copper(II)-benzothiazolamine complex.