AbstractStability constants have been measured for a series of ligands based on a 2,2′‐(pyridine‐2,6‐diyl)bis[1H‐benzimidazole] unit which forms dinuclear double‐stranded helical complexes with copper(I). Variation of different structural parameters confirms the importance of the coordinate bond, the stacking interactions, and the weakly bridging pyridine units observed by X‐ray crystallography. The stabilities of the complexes depend strongly on the solvent, and in MeCN, which is a good solvent for copper(I), the complexes are less stable and assemble in a stepwise manner. The interconversion of the enantiomers may be followed by1H‐NMR and takes place on a millisecond time scale around room temperature. The trends in lability are similar to those found for the stability o