Polyelectrolyte complexes between poly(methacrylic acid, sodium salt) and poly(diallyldimethylammonium chloride) (PDADMAC) or poly[2‐(methacryloyloxyethyl)trimethylammonium chloride] (PMOETAC) form gels, liquid phases, or soluble complexes depending on charge ratio, total polymer loading, polymer molecular weight, and ionic strength. Increasing the ionic strength of the medium led most polyelectrolyte pairs to transition from gel through liquid complexes (complex coacervate) to soluble complexes. These transitions shift to higher ionic strengths for higher molecular weight polymers, as well as for PMOETAC compared to PDADMAC. The complex phases swelled with increasing polymer loading, ultimately merging with the supernatant phase at a critical polymer loading. The isolated liquid complex phases below and above this critical loading were temperature‐sensitive, showing cloud points followed by macroscopic phase separation upon heating. Incorporating 5 mol % lauryl methacrylate into the polyanion led to increased complex yield with PDADMAC, and increased resistance to ionic strength. In contrast, incorporating 30 mol % of oligo(ethylene glycol) methacrylate into the polyanion led to decreased complex yield, and to lower resistance to ionic strength. Two polyelectrolyte systems that produced liquid complexes were used to encapsulate hydrophobic oils, and in one case were used to demonstrate the feasibility of crosslinking the resulting capsule walls. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4129–4143, 2007 Complexation of PMAANa with the quaternary ammonium polycations PDADMAC or PMOETAC lead to either gelled, liquid or soluble polyelectrolyte complexes, depending on charge ratio, polymer loading, molecular weight, and ionic strength. The complex phases swelled with increasing polymer loading, and merged with the supernatant phase at a critical loading. The liquid complex phases near this critical loading phase separate upon heating. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]