Perfluorinated alcohols and acids such as hexafluoroisopropanol (HFIP), trifluoroethanol, trifluoroacetic acid, pentafluoropropionic acid, and heptafluorobutyric acid induce coacervation and phase separation in aqueous solutions of a wide variety of individual and mixed amphiphiles [Khaledi et al. Langmuir 2013, 29, 2458]. This paper focuses on HFIP-induced complex coacervate formation in the mixtures of anionic polyelectrolytes, such as sodium salt of poly(methacrylic acid) (PMA) or poly(acrylic acid) (PAA) and cationic surfactants alkyltrimethylammonium bromides. In purely aqueous media and over a wide concentration range, mixtures of PMA and CTAB form the catanionic complex (CTA(+)PM(-)) that is insoluble in water (white precipitate). Upon addition of a small percentage of HFIP, the mixture goes through phase transition and formation of two distinctly clear liquid phases. The phase diagram for the HFIP-MA-TAB coacervate system was studied. The coacervate volume was determined as a function of system variables such as charge ratio as well as total and individual concentrations of the system components. These results, combined with the chemical composition analysis of the separated aqueous top-phase and coacervate bottom-phase, shed light on the coacervation mechanism. The results suggest that exchange of counterions and ion-pair formation play critical roles in the coacervation process. This process facilitated by HFIP through solvation of the head groups and dehydration of the hydrophobic moieties of the catanionic complex. Because of the presence of HFIP, coacervation occurs over a wide range of concentrations and charge ratios of the oppositely charged polyelectrolyte and surfactant.