A complex with the formula [CuL(H2O)2]{[CuL][Fe(CN)6]}2·2H2O, where L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, has been synthesized and crystallographically characterized. The structure is composed of a one-dimensional zigzag chain of $$\left\{ {[{\text{CuL}}][{\text{Fe(CN)}}_{\text{6}} ]} \right\}_2^{2 - } $$ units, and [CuL(H2O)2]2+ units. The one-dimensional zigzag chain extents through $${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Fe}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Cu}}$$ linkages. The adjacent two polymer chains are linked by the $${\text{O}}{\kern 1pt} - {\kern 1pt} {\text{H}}{\kern 1pt} \cdot \cdot \cdot {\kern 1pt} {\text{N}}{\kern 1pt} \equiv {\kern 1pt} {\text{C}}{\kern 1pt} - $$ hydrogen bonding between [CuL(H2O)2]2+ and [Fe(CN)6]3−, forming a 3D supramolecular structure with inner hydrophilic channels. Magnetic susceptibility measurements show no exchange interaction between the Cu(II) and Fe(III) ions due to the longer $${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{N}}$$ (axial) bond length.