A molecular dynamics study has been carried out to investigate the conformational, structural and dynamical properties of the surfactant molecules in the dodecyltrimethylammonium·poly(α,l-glutamate) self-assembled complex. Simulations were performed in chloroform solution using eight different temperatures. Results indicate that the strong electrostatic interactions between the carboxylate groups of the polyelectrolyte and the positively charged trimethylammonium moieties, which are retained even at high temperatures, are responsible of the molecular organization and the low mobility of the surfactant molecules.