Electrochemical polymerisation of 2-aminofluorene, 2AF, was investigated in ethylalcohol/water mixture (3:2, v:v) in the presence of HClO4 as the supporting electrolyte via constant potential electrolysis, CPE. Prior to CPE, electrochemical behaviour of the monomer was investigated in the same solvent electrolyte couple utilising cyclic voltammetry, CV. Electrochemical polymerisation of the monomer yielded insoluble, dark bluish-green, conducting polymer deposit on the electrode surface. Characterisation of the polymer film has been carried out using FT-IR spectroscopic technique and thermal behaviour was studied using differential scanning calorimetry, DSC. Spectroelectrochemical, SPEL, behaviour of the polymer on ITO working electrode was studied by recording the electronic absorption spectra, in situ, in monomer-free solution at different potentials and it is found that the film can be reversibly cycled between -0.1 and 1.1 V vs SCE. Paramagnetic behaviour of the polymer was monitored using in situ ESR spectroscopy. The temperature dependence of conductivity supported the Mott's variable range hopping, VRH, mechanism for poly(aminofluorene), PAF. (C) 2004 Elsevier Ltd. All rights reserved.