Conjugated polyelectrolytes (CPEs), which combine π-conjugated backbones with ionic side chains, are intrinsically soluble in polar solvents and have demonstrated tunability with respect to solution processability and optoelectronic performance. However, this class of polymers often suffers from limited solubility in water. Here, we demonstrate how polyelectrolyte coacervation can be utilized for aqueous processing of conjugated polymers at extremely high polymer loading. Sampling various mixing conditions, we identify compositions that enable the formation of complex coacervates of an alkoxysulfonate-substituted PEDOT (PEDOT-S) with poly(3-methyl-1-propylimidazolylacrylamide) (PA-MPI). The resulting coacervate is a viscous fluid containing 50% w/v polymer and can be readily blade-coated into films of 4 ± 0.5 μm thick. Subsequent acid doping of the film increased the electrical conductivity of the coacervate to twice that of a doped film of neat PEDOT-S. This higher conductivity of the doped coacervate film suggests an enhancement in charge carrier transport along PEDOT-S backbone, in agreement with spectroscopic data, which shows an enhancement in the conjugation length of PEDOT-S upon coacervation. This study illustrates the utilization of electrostatic interactions in aqueous processing of conjugated polymers, which will be useful in large-scale industrial processing of semiconductive materials using limited solvent and with added enhancements to optoelectronic properties.