The widespread of mixtures formed by polyelectrolytes and oppositely charged surfactants in different industrial sectors requires a thorough understanding of the physicochemical bases governing their interactions. These interactions lead to the formation of polyelectrolyte–surfactant aggregates, with the presence of such aggregates in the aqueous mixtures impacting decisively on their bulk and interfacial properties. Furthermore, the broad range of morphologies, sizes, and properties of the aggregates makes it necessary to obtain a comprehensive picture describing their behavior and properties to be able to exploit their possible applications. This review is aimed to shed light on some of the most relevant physicochemical aspects involved in the complexation process of polyelectrolyte–surfactant mixtures, paying special attention to the formation of nonequilibrium states (kinetically trapped aggregates), and how these impact on the interaction of the complexes with interfaces, both fluid/fluid and solid/fluid.

由聚电解质和带相反电荷的表面活性剂形成的混合物在不同的工业领域中的广泛使用，需要对控制它们之间相互作用的物理化学基础有透彻的了解。这些相互作用导致聚电解质-表面活性剂聚集体的形成，水性混合物中此类聚集体的存在对它们的体积和界面性质产生决定性的影响。此外，聚集体的形貌，尺寸和性质范围广泛，因此有必要获得一张描述其行为和性质的综合图，以便能够利用其可能的应用。这篇综述旨在阐明与聚电解质-表面活性剂混合物的络合过程有关的一些最相关的物理化学方面，