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The title compound, {(C6H14N2O2)[Cu2Cl6(H2O)]}n, consists of 1,4-dihydroxy-1,4-diazoniabicyclo[2.2.2]octane dications and one-dimensional inorganic anionic {[Cu2Cl6(H2O)]2−}n chains in which both five-coordinate [CuCl3(H2O)] and five-coordinate [CuCl3] units exist. These two distinct type of unit are linked together by one chloride ion and are bridged across centres of inversion to further units of their own type through two chloride ions, giving rise to novel polymeric zigzag chains parallel to the c axis. The chains are connected by O—H...Cl hydrogen bonds to produce R24(16) ring motifs, resulting in two-dimensional layers parallel to the ac plane. These layers are linked into a three-dimensional framework with the organic cations via O—H...Cl hydrogen bonds. Hydrogen bonding between the chains, and between the chains and the organic cations, provides stability to the crystal structure.