Redox transformation of electronically conducting polymers was studied by different in situ combined electrochemical techniques. Results obtained with polypyrrole/dodecyl sulfate film in aqueous solution and with polythiophene/hexafluorophosphate films in acetonitrile by in situ ac conductance and EQCM support the assumption of the key role of the desolvation in the achievement of the so-called quasi-metallic state of electronically conducting polymers. The desolvation considered as a phase transition is the chemical background of the capacitive behaviour, and it causes the structural changes, which lead to a film in which the interchain interactions may form the large-scale conducting polymer matrix. (C) 2004 Elsevier Ltd. All rights reserved.