A novel and simple method of preparation of a conducting network, by physical crosslinking of microgel particles of poly(3,4-ethylenedioxythiophene) (PEDOT), has been presented. PEDOT doped with excess of polystyrenesulphonate (PSS) has excess negative charge, which was used to form ionic bonds with multivalent cations for the physical crosslinking. Crosslinked polymer shows excellent electrochemical properties in aqueous medium due to high ionic mobility in the material. It has been shown that such method of physical crosslinking may be used to prepare blends with network morphology of the conducting component. This leads to high conductivity of the blend, even at low loading of the conducting component.