We report the synthesis and crystal structure of a copper (II) polymeric complex (I) prepared by reaction of Cu(ClO₄)₂ ·5H₂O with H₃tea (triethanolamine,) and dpe (1,2-di(4-pyridyl)ethylene). in ethanol. The compound is made up of two well differentiated substructures, the first one being a cationic 1D polymer balanced by ClO₄^- counteranions {[Cu₂(H₂tea)₂(dpe)]·(ClO₄)₂}_n and the second one made is up of two dimers of different occupancies and charge content, viz., [Cu₂(Htea)₂(dpe)] (neutral, 64% occupancy) and [Cu₂(H₂tea)₂(dpe)]²⁺ (cationic, 36% occupancy), this latter fraction balancing the charge introduced by ClO₄^- anions with 72% occupancy. Both substructures differ in that the H_mtea anions in the dimers (m = 1,2) do not bridge cations as their homologue H₂tea does in the polymer, but chelate instead one single Cu each. As shown in scheme. The structure of (I) is compared with its close relative [Cu₂(H₂tea)₂(dpe)]·(bpe)·(ClO₄)₂·H₂O (II), where the same original constituents assemble in a slightly different way.