Studying the interactions of biopolymers like polysaccharides and proteins is quite important mainly due to the wide number of applications such as the stabilization and encapsulation of active compounds in complex systems. Complexation takes place when materials like proteins and polysaccharides are blended to promote the entrapment of active compounds. The interaction forces between the charged groups in the polymeric chains allow the miscibility of the components in the complex system. Understanding the interactions taking place between the polymers as well as between the wall material and the active compound is important when designing delivery systems. However, some features of the biopolymers like structure, functional groups, or electrical charge as well as extrinsic parameters like pH or ratios might affect the structure and the performance of the complex system when used in encapsulation applications. This work summarizes the recent progress of the polysaccharide/protein complexes for encapsulation and the influence of the pH on the structural modifications during the complexation process. Display omitted •pH is an important parameter that determines the molecular assembly.•The molecular association is due to electrostatic and weaker interactions.•The entrapment can take place by overlaying, inclusion, or a mixed effect of molecules.