Poly(1,8-diaminonaphthalene) films, p(1,8-DAN), were electrosynthesized on a Pt electrode to study their utility in extracting Cr(VI) ( as dichromate ions) from acidic aqueous solution. The electrodeposition procedure was improved by acidification of the acetonitrile electropolymerisation bath with CCl3COOH. Possible molecular structures of electrosynthesized poly(1,8-diaminonaphthalene) were determined by means of IR spectroscopy. The mechanism of dichromate ion removal was studied by potentiometric measurements in the system Ag/AgCl/Cl-(std)(-)/0.1 M HClO4/ p(1,8-DAN)/Pt, upon addition of K2Cr2O7 solution. The presence and oxidation state of chromium in the polymer matrix was explored by means of energy dispersive X-ray (EDX) spectrometry.