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The adsorption of mixtures of poly(diallyldimethylammonium chloride) (PDADMAC) and sodium N-lauroyl-N-methyltaurate (SLMT) at the water / vapor interface has been studied using drop profile tensiometry and neutron reflectometry. This study sheds light on the mechanisms involved in the adsorption of polyelectrolyte-oppositely charged surfactants by the characterization of both equilibrium and dynamics features associated with the layer formation at the fluid interface. The results are discussed in terms of an adsorption-equilibration of the interfacial layers as a two-step process: the initial stages involve the adsorption of polyelectrolyte-surfactant complexes formed in the bulk, and a subsequent stage involves reorganization of the interface. This work contributes to the understanding of the physico-chemical features of systems that undergo complex bulk and interfacial interactions with importance in science and technology.