The current challenges in the food packaging field are, on one side, replacing plastic from non-renewable sources with biopolymers and, on the other hand, generating a packaging material with attractive properties for the consumer. Nowadays, the consumer is concerned ecologically; the food packaging industry must ahead satisfy their needs. In this sense, incorporating several compounds with properties such as antioxidant, antimicrobial, or nutraceutical properties results attractive for the consumers. However, many of these properties can be diminished, so an encapsulation system is required. A good encapsulating system is crucial for these purposes, so polyelectrolyte complexes (PECs) can be used with that finality. Nowadays, PECs are eye-catching in many fields because of their fascinating properties, which make them very attractive, mainly for being used as encapsulating systems. Hence, this paper reviews the use of PECs in food packaging where chitosan forms polyelectrolyte complexes.