This work is aimed at the analysis of the interactions that drive the assembling of coordination metal-organic polymers based on biological molecules. Single-crystal X-ray diffraction data show that the compound 1D-{[Cu2(μ-ade)4(H2O)2]·2[Cu(theoph)2]·∼10H2O}n (1) contains neutral rhomboid shaped chains sustained by the tridentate μ3-κN3:κN7:κN9 coordination mode of the adenine nucleobase. These chains are formed by dimeric copper/adeninato (ade) cores doubly bridged by monomeric copper/theophyllinato (theoph) entities with the alkaloid acting as peripheral ligand. The lack of direct intermolecular nucleobase···nucleobase interactions, due to their disruption by the crystallization water molecules, does not provide a highly porous material, but the irregular shape of the polymeric chain hinders their packing and allows the presence of a moderate amount of voids (16% of the unit cell volume) in good accordance with its adsorption capacity of 0.38 mmol CO2/g at 273 K. Thermogravimetric and variable temperature X-ray diffraction analyses show that the compound retains its structure up to 110 °C whereas above this temperature the release of the coordination water molecules produces a significant loss of crystallinity. Magnetic measurements indicate an overall antiferromagnetic behavior with a J value of −267 cm−1 within the dimeric entity.