The aim of this work was to elaborate on a thin polymeric film for coating transparent fluorine-doped tin oxide (FTO) electrode supported on a glass substrate for trapping Cu2+ ions. Possible applications are the easier detection of Cu2+ ions due to complexation on the FTO surface or could be the making up of electrochromic devices using copper(I)-salt based electrolytes to avoid diffusion of Cu2+ ions formed at the anode toward Cu(0) deposited on the cathode. These thin polymeric films proposed here as complexing material candidates toward copper ions belong to polyalkyleneimine polymers. They were obtained by anodic electropolymerization of aliphatic polyamines (with at least two primary amino groups) such as ethylenediamine, 1,3-diaminopropane, or diethylenetriamine on FTO electrode surfaces and characterized by IR attenuated total reflectance spectroscopy. Moreover, we have shown that polyalkyleneimine-type polymers used here present good chelating properties towards Cu2+ ions due to the amino groups they contain.