Polyelectrolyte complexes (PECs) formed from mixtures of polycations and polyanions are useful in a variety of applications and can be processed by the addition of salt. Salt mediates the ionic interactions within the polyelectrolyte complexes, with appropriately chosen salts enabling complete dissolution of solid PEC in aqueous media. Substantial complications arise from the crystallization of the salt during subsequent processing steps. Here we show that appropriately chosen noncrystallizing deep eutectic solvents can be used to process solid PECs. Mixtures of ethylene glycol and guanidine thiocyanate are used for a particularly effective deep eutectic solvent. The phase behaviors of this deep eutectic system and of its mixtures with a model polyelectrolyte complex were quantified.