The metalloligand approach was used to obtain a novel Cu II /Zn II heterobimetallic coordination polymer (CP) 1, based on the carefully designed bispidine ligand L4. CP 1, characterized by single crystal (SC-) and powder X-ray diffraction methods (P-XRD), is constituted by repeating large 32-membered macrocycles forming ribbon-like linear arrays and it features a Cu IIcoordination site occupied by a markedly labile MeCN. We also describe the synthesis and characterization of intermediate metalloligands (with Cu II , Fe III , Mn II , and Pd II , the latter three obtained as SCs and characterized accordingly) and provide a view of potential intermediate species along the route from metalloligands to heterometallic CPs.