The complexation of oppositely charged conjugated polyelectrolytes, which combine π-conjugated backbones with pendant ionic groups, offers an opportunity for the development of large-scale, flexible, and biocompatible organic electronics using simple fabrication methods such as roll-to-roll printing. The phase behavior of a model system of donor-acceptor conjugated polyelectrolytes of the same π-conjugated backbone, but oppositely charged pendant groups (pyridinium⁺ and sulfonate^-) demonstrates the importance of solvent quality and charge balance. Regions of two-phase liquid-liquid separation as well as soft-solidification create highly concentrated soft materials of the active components, providing an opportunity for the production of thick films during roll-to-roll printing. These dense phases amplify interactions between the conjugated backbones, resulting in increased charge transfer throughout the network.