Quantitative in-situ EPR spectroelectrochemical studies of poly(3,4-ethylenedioxythiophene) (PEDOT) have been carried out with an aim to gain new insights into the doping processes taking place in this polymer. Corroborating the findings made during previous studies of this polymer, absolute measurements conducted in this study provided new detailed information regarding some of the basic parameters characterising the doping process of this conjugated polymer. It was found that concentrations of paramagnetic centres in PEDOT vary from 0.02 spin per mer in the dedoped state up to a maximum of 0.12 spin per mer at 0.15 [e(-)/mer] doping level, corresponding to 1 spin per ca. 8.5 meric units. Such notable concentration values indicate that polarons represent a numerous charge carrier group in PEDOT, contrary to observations made for other members of polythiophene family. Furthermore polarons do not disappear at high doping levels of PEDOT but rather decrease their numbers gradually down to 0.08 spins per mer at a maximum doping level of 0.55 [e(-)/mer] attained in this study. Based on information about concentrations of spins and polymer doping charges, concentrations of bipolarons have been evaluated as a function of doping level. Results indicate that bipolaron formation starts at ca. 0.06 [e(-)/merl doping level when spin generation efficiency begins to deviate from 1 and interspin interactions emerge as evidenced by doping level dependency of EPR signal linewidth (Delta B-pp). Decomposition of complex EPR spectra of PEDOT in its doped state corroborated the presence of two groups of paramagnetic centres in this polymer. Based upon doping level dependencies of their spectroscopic parameters (concentration, Delta B-pp linewidth and g-factor), the identity of these centres has been redefined compared to our previous reports, linking their properties with the type of polymer phase (crystalline or amorphous) they reside in. (c) 2008 Elsevier Ltd. All rights reserved.