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We report here a systematic study on the phase behavior of dodecyltrimethylammonium-poly(acrylate) (C12TAPA) complex salts upon addition of simple salts (NaBr and NaCl). Complex salts of poly(acrylate) of two molar masses were employed (2000 and 450,000 g mol-1). Systems containing different surfactant mesophases were observed, whose structures were elucidated by small-angle X-ray scattering analyses. Overall, we observe a transition from associative to segregative phase separation intercalated with monophasic regions. In terms of surfactant association, a