Hydrogen bonded coordination polymers, {[Cu(CA)(H2O)(2)](H2O)}(n), [Cu(CA)(MeOH)(2)](n), (H(2)CA; chloranilic acid), and related polycrystalline analogs have been structurally and magnetically characterized. 1-Dimensional (1-D) weak antiferromagnetic exchange interaction (J = -2.01 cm(-1)) was observed in {[Cu(CA)(H2O)(2)](H2O)}(n), which has a 3-dimensional hydrogen bond network in the crystal. This polycrystalline form liberates the water molecules to be [Cu(CA)](n), which is known as the Heisenberg antiferromagnet. Powder X-ray diffraction and thermal data show that the framework constructed by 1-D chains are so stable that water molecules readily come out without breaking the 1-D chains. Two types of coordination polymers ([Cu(CA)(MeOH)(2)](n), and [Cu(CA)(MeOH)](n)) containing axially coordinated MeOH have been prepared. [Cu(CA)(MeOH)](n), has strong and anomalous antiferromagnetic exchange interactions in the crystal, indicating a new phase of Cu/CA systems, such as a mixed valence state, and if so the coordinated MeOH plays an important role to control physical ploperties of the polymers.