Polydentate ligands 1 and 2, which incorporate a terminal pyridyl moiety and an oxygen‐rich oxalate dihydrizide/malonic dihydrizide spacer moiety, as well as their binuclear metal complexes [Cu212] and [Cu222], which adopt a 1:1 metal/ligand ratio, were synthesized and characterized. Both complexes were screened for their catalytic activity in the nitroaldol reaction, in which [Cu212] worked efficiently as catalyst for both substituted benzaldehyde and pyridinecarboxaldehyde, whereas [Cu222] is highly substrate specific and showed activity towards nitro‐substituted aldehydes and pyridinecarboxaldehyde. Furthermore, as helicates are intrinsically chiral, the stereochemical architecture in the binuclear double‐stranded Cu2 helicates as catalyst favored the diastereoselective syn product with nitroethane and nitropropane and their respective diastereoselectivities were determined by using 1H NMR spectroscopy.