Poly(dibenzo-18-crown-6) (poly-DB18C6) was synthesized by electrochemical oxidation of dibenzo-18-crown-6 (DB18C6) using a mixture of acetonitrile and dichloromethane as the solvent and tetrabutylammonium tetrafluoroborate (TBABF(4)) or tetrabutylammonium hexafluorophosphate (TBAPF(6)) as supporting electrolyte. The anodic polymerization of DB18C6 was investigated using in situ ESR and in situ UV-Vis spectroscopic techniques. Spectroelectrochemical (SPEL), properties and thermal analysis of the resulting polymers have been investigated using UV-Vis spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). (C) 2004 Elsevier B.V. All rights reserved.