Coordination polymer networks, [Cu₂(C₂₆H₅₂N₁₀)(BDC)₂]·4H₂O (1) and [Cu₂(C₂₆H₅₂N₁₀)(BDC)₂]·2DHB·4H₂O (2) with 2D brick-wall structures, [Cu₂(C₂₆H₅₂N₁₀)(BDC)₂]·4HB·4H₂O (3) with a 1D ladder structure, and [Cu₂(C₂₆H₅₂N₁₀)(BDC)(H₂O)₂]·2(THB)-(BDC)·8H₂O (4) with a 1D chain structure, have been assembled in water from a Cu^II bismacrocyclic complex [Cu₂(C₂₆H₅₂N₁₀)(Cl)₄]·6H₂O (A) and sodium 1,4-benzenedicarboxylate (Na₂BDC) in the presence of no organic guest for 1, 1,4-dihydroxybenzene (DHB) for 2, hydroxybenzene (HB) for 3, and 1,3,5-trihydroxybenzene (THB) for 4. In the assembly of the networks, the guest molecule acts as a template and stabilizes the host structure by the hydrogen bonding or π–π stacking interactions. In addition, the guest molecules interact with each other as well as with the host to form 1D columns that occupy the channels in 1, 2, and 3, and the 2D noncovalent organic layers that are alternately packed with the host layers in 4.