AbstractN,N‐bis(carboxymethyl)‐1‐adamantylamine acid (H2BCAA) or N‐(1‐adamantyl)‐iminodiacetic acid forms zwitterions that are intra‐stabilized by a ‘bifurcated’ N+‐H···O(carboxyl)2 interaction. In the crystal, both half‐protonated carboxyl groups of H2BCAA± are involved in linear O‐H···O inter‐molecular bridges of 2.46Å. In the studied BCAA‐CuII derivatives, the iminodiacetate‐moiety of the BCAA chelating ligand exhibits a mer‐NO2 conformation in [Cu(BCAA)(H2O)2] (1) and [Cu(BCAA)(Him)]2 (2), but a fac‐O2+N(apical) conformation in [Cu(BCAA)(bpy)(H2O)]·3.5H2O (3) [Him = imidazole, bpy =2,2′‐bipyridine]. In clear contrast, dipyridylamine (dpya), as auxiliary ligand, seems to be unable to promote the fac‐O2+N(apical) conformation in BCAA, as reveal the structures of two new salts with the trinuclear cation [(dpya)2Cu‐μ2‐Cu(BCAA)2‐Cu(dpya)2]2+ and the anions [Cu(BCAA)2]2− (4) or NO3− (5), respectively.