The adsorption of concentrated poly(diallyldimethylammonium chloride) (PDADMAC)-sodium lauryl ether sulfate (SLES) mixtures at the water/vapor interface has been studied by different surface tension techniques and dilational viscoelasticity measurements. This work tries to shed light on the way in which the formation of polyelectrolyte-surfactant complexes in the bulk affects the interfacial properties of mixtures formed by a polycation and an oppositely charged surfactant. The results are discussed in terms of a two-step adsorption-equilibration of PDADMAC-SLES complexes at the interface, with the initial stages involving the diffusion of kinetically trapped aggregates formed in the bulk to the interface followed by the dissociation and spreading of such aggregates at the interface. This latter process becomes the main contribution to the surface tension decrease. This work aids our understanding of the most fundamental basis of the physicochemical behavior of concentrated polyelectrolyte-surfactant mixtures which present complex bulk and interfacial interactions with interest in both basic and applied sciences.