Communication: Enhanced conductivity in conjugated polymer blends can be achieved by supramolecular self-assembly. The authors demonstrate that the morphology of the conducting polymer blend can be modified by crosslinking of one of its components. Ionic crosslinking of the conducting component-poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT-PSS)-is shown to result in a three-dimensional network and an increase in the electrical conductivity by a few orders of magnitude. For the ionic crosslinking a bivalent cation, such as Mg2+, is used.